EP2414432A2 - Amine-terminated telechelic polymers and precursors thereto and methods for their preparation - Google Patents
Amine-terminated telechelic polymers and precursors thereto and methods for their preparationInfo
- Publication number
- EP2414432A2 EP2414432A2 EP10762101A EP10762101A EP2414432A2 EP 2414432 A2 EP2414432 A2 EP 2414432A2 EP 10762101 A EP10762101 A EP 10762101A EP 10762101 A EP10762101 A EP 10762101A EP 2414432 A2 EP2414432 A2 EP 2414432A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- compound
- pyrrole
- hydrogen
- group
- pib
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 84
- 229920006250 telechelic polymer Polymers 0.000 title claims abstract description 29
- 239000002243 precursor Substances 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 title description 3
- -1 N-substituted pyrrole compounds Chemical class 0.000 claims abstract description 72
- 150000001422 N-substituted pyrroles Chemical class 0.000 claims abstract description 64
- 229920002367 Polyisobutene Polymers 0.000 claims description 152
- 238000006116 polymerization reaction Methods 0.000 claims description 84
- 239000001257 hydrogen Substances 0.000 claims description 69
- 229910052739 hydrogen Inorganic materials 0.000 claims description 69
- 239000000203 mixture Substances 0.000 claims description 69
- 239000003999 initiator Substances 0.000 claims description 67
- 150000001875 compounds Chemical class 0.000 claims description 64
- 125000003118 aryl group Chemical group 0.000 claims description 57
- 239000000178 monomer Substances 0.000 claims description 54
- 125000000217 alkyl group Chemical group 0.000 claims description 51
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 49
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 42
- 239000002841 Lewis acid Substances 0.000 claims description 39
- 150000007517 lewis acids Chemical class 0.000 claims description 38
- 239000003153 chemical reaction reagent Substances 0.000 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 239000003921 oil Substances 0.000 claims description 23
- 150000002431 hydrogen Chemical group 0.000 claims description 22
- 239000010687 lubricating oil Substances 0.000 claims description 15
- 229920000098 polyolefin Polymers 0.000 claims description 14
- 150000001336 alkenes Chemical group 0.000 claims description 12
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 12
- 239000012141 concentrate Substances 0.000 claims description 12
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 11
- 239000003085 diluting agent Substances 0.000 claims description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 230000001050 lubricating effect Effects 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 161
- 238000010791 quenching Methods 0.000 abstract description 69
- 230000000171 quenching effect Effects 0.000 abstract description 66
- 150000001412 amines Chemical class 0.000 abstract description 16
- 125000000524 functional group Chemical group 0.000 abstract description 11
- 125000002091 cationic group Chemical group 0.000 abstract description 4
- 229920013730 reactive polymer Polymers 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 234
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 150
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 122
- 238000006243 chemical reaction Methods 0.000 description 79
- 239000000047 product Substances 0.000 description 61
- 239000000243 solution Substances 0.000 description 45
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 43
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 41
- 125000000168 pyrrolyl group Chemical group 0.000 description 38
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 36
- 238000007306 functionalization reaction Methods 0.000 description 34
- 239000000654 additive Substances 0.000 description 33
- 230000015572 biosynthetic process Effects 0.000 description 29
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 29
- 125000001246 bromo group Chemical group Br* 0.000 description 27
- 125000004093 cyano group Chemical group *C#N 0.000 description 25
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- 239000002270 dispersing agent Substances 0.000 description 23
- 230000010354 integration Effects 0.000 description 22
- 125000001309 chloro group Chemical group Cl* 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 21
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 20
- 238000006467 substitution reaction Methods 0.000 description 19
- 230000000996 additive effect Effects 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 18
- 238000011065 in-situ storage Methods 0.000 description 18
- 239000012299 nitrogen atmosphere Substances 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 17
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 16
- 238000010538 cationic polymerization reaction Methods 0.000 description 16
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000003599 detergent Substances 0.000 description 15
- 238000011067 equilibration Methods 0.000 description 15
- 238000010550 living polymerization reaction Methods 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 238000004458 analytical method Methods 0.000 description 14
- 238000005859 coupling reaction Methods 0.000 description 14
- 150000002148 esters Chemical class 0.000 description 14
- 239000012530 fluid Substances 0.000 description 14
- 230000008034 disappearance Effects 0.000 description 12
- 238000004090 dissolution Methods 0.000 description 12
- 238000007345 electrophilic aromatic substitution reaction Methods 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 12
- 239000000523 sample Substances 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 11
- 238000009826 distribution Methods 0.000 description 11
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 10
- 239000000446 fuel Substances 0.000 description 10
- 230000006870 function Effects 0.000 description 10
- 125000001183 hydrocarbyl group Chemical group 0.000 description 10
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 150000004820 halides Chemical class 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 239000012038 nucleophile Substances 0.000 description 9
- 150000003233 pyrroles Chemical class 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 9
- 238000012546 transfer Methods 0.000 description 9
- HJFZAYHYIWGLNL-UHFFFAOYSA-N 2,6-DiMepyz Natural products CC1=CN=CC(C)=N1 HJFZAYHYIWGLNL-UHFFFAOYSA-N 0.000 description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical group Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 8
- 230000036961 partial effect Effects 0.000 description 8
- 238000012667 polymer degradation Methods 0.000 description 8
- 239000004071 soot Substances 0.000 description 8
- KLIDCXVFHGNTTM-UHFFFAOYSA-N syringol Natural products COC1=CC=CC(OC)=C1O KLIDCXVFHGNTTM-UHFFFAOYSA-N 0.000 description 8
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 8
- QBAVHEZVBGASER-UHFFFAOYSA-N 1-(2-bromoethyl)pyrrole Chemical compound BrCCN1C=CC=C1 QBAVHEZVBGASER-UHFFFAOYSA-N 0.000 description 7
- 229910015844 BCl3 Inorganic materials 0.000 description 7
- 150000002170 ethers Chemical class 0.000 description 7
- 239000002816 fuel additive Substances 0.000 description 7
- 125000001072 heteroaryl group Chemical group 0.000 description 7
- 239000011968 lewis acid catalyst Substances 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000003342 alkenyl group Chemical group 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 230000008878 coupling Effects 0.000 description 6
- 238000010168 coupling process Methods 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- YPHWIAIHNIRRHU-UHFFFAOYSA-N 1-tert-butyl-3,5-bis(2-chloropropan-2-yl)benzene Chemical compound CC(C)(C)C1=CC(C(C)(C)Cl)=CC(C(C)(C)Cl)=C1 YPHWIAIHNIRRHU-UHFFFAOYSA-N 0.000 description 5
- LODOULPXKZPVQI-UHFFFAOYSA-N 2,6-dichloro-2,4,4,6-tetramethylheptane Chemical compound CC(C)(Cl)CC(C)(C)CC(C)(C)Cl LODOULPXKZPVQI-UHFFFAOYSA-N 0.000 description 5
- MJMQIMYDFATMEH-UHFFFAOYSA-N 2-chloro-2,4,4-trimethylpentane Chemical group CC(C)(C)CC(C)(C)Cl MJMQIMYDFATMEH-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 235000019341 magnesium sulphate Nutrition 0.000 description 5
- 230000000269 nucleophilic effect Effects 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000001902 propagating effect Effects 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 5
- WGECXQBGLLYSFP-UHFFFAOYSA-N (+-)-2,3-dimethyl-pentane Natural products CCC(C)C(C)C WGECXQBGLLYSFP-UHFFFAOYSA-N 0.000 description 4
- CXOWYJMDMMMMJO-UHFFFAOYSA-N 2,2,4-trimethyl-butane Natural products CCCC(C)(C)C CXOWYJMDMMMMJO-UHFFFAOYSA-N 0.000 description 4
- BZHMBWZPUJHVEE-UHFFFAOYSA-N 2,3-dimethylpentane Natural products CC(C)CC(C)C BZHMBWZPUJHVEE-UHFFFAOYSA-N 0.000 description 4
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 4
- UWKQJZCTQGMHKD-UHFFFAOYSA-N 2,6-di-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=N1 UWKQJZCTQGMHKD-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- AEXMKKGTQYQZCS-UHFFFAOYSA-N Dimethyl-diaethyl-methan Natural products CCC(C)(C)CC AEXMKKGTQYQZCS-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 235000006708 antioxidants Nutrition 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 125000002950 monocyclic group Chemical group 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 230000008719 thickening Effects 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 3
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 3
- IXIXPLRTYIMRMC-UHFFFAOYSA-N 1-(3-bromopropyl)pyrrole Chemical compound BrCCCN1C=CC=C1 IXIXPLRTYIMRMC-UHFFFAOYSA-N 0.000 description 3
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 3
- MRFQFQYRTNGOCZ-UHFFFAOYSA-N 2-methoxypropan-2-ylbenzene Chemical compound COC(C)(C)C1=CC=CC=C1 MRFQFQYRTNGOCZ-UHFFFAOYSA-N 0.000 description 3
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229930006722 beta-pinene Natural products 0.000 description 3
- 239000012455 biphasic mixture Substances 0.000 description 3
- 229910000085 borane Inorganic materials 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 208000012839 conversion disease Diseases 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- DDEYRIPSENAFHO-UHFFFAOYSA-N diazonio(2-pyrrol-1-ylethyl)azanide Chemical compound [N-]=[N+]=NCCN1C=CC=C1 DDEYRIPSENAFHO-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000006078 metal deactivator Substances 0.000 description 3
- 238000006011 modification reaction Methods 0.000 description 3
- 150000002825 nitriles Chemical group 0.000 description 3
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 3
- 238000005580 one pot reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 238000011002 quantification Methods 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- HYWCXWRMUZYRPH-UHFFFAOYSA-N trimethyl(prop-2-enyl)silane Chemical compound C[Si](C)(C)CC=C HYWCXWRMUZYRPH-UHFFFAOYSA-N 0.000 description 3
- 229920002554 vinyl polymer Chemical group 0.000 description 3
- NRGJLOLQAOMGHN-UHFFFAOYSA-N (2,4,4,6-tetramethyl-6-propanoyloxyheptan-2-yl) propanoate Chemical compound CCC(=O)OC(C)(C)CC(C)(C)CC(C)(C)OC(=O)CC NRGJLOLQAOMGHN-UHFFFAOYSA-N 0.000 description 2
- ICLIEMBQKDJYBV-UHFFFAOYSA-N (6-acetyloxy-2,4,4,6-tetramethylheptan-2-yl) acetate Chemical compound CC(=O)OC(C)(C)CC(C)(C)CC(C)(C)OC(C)=O ICLIEMBQKDJYBV-UHFFFAOYSA-N 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 description 2
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- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- FYRHIOVKTDQVFC-UHFFFAOYSA-M potassium phthalimide Chemical compound [K+].C1=CC=C2C(=O)[N-]C(=O)C2=C1 FYRHIOVKTDQVFC-UHFFFAOYSA-M 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000005377 tertiary alkyl halides Chemical class 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- CEWUOVYLVVHIPP-UHFFFAOYSA-N thiadiazole;1,2-thiazole Chemical compound C=1C=NSC=1.C1=CSN=N1 CEWUOVYLVVHIPP-UHFFFAOYSA-N 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical class [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical compound [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-UHFFFAOYSA-L 0.000 description 1
- 238000007693 zone electrophoresis Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
- C10M133/58—Heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2810/00—Chemical modification of a polymer
- C08F2810/40—Chemical modification of a polymer taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/30—Heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/04—Detergent property or dispersant property
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/04—Detergent property or dispersant property
- C10N2030/041—Soot induced viscosity control
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2070/00—Specific manufacturing methods for lubricant compositions
Definitions
- N-substituent contains a functional group that may be derivatized to basic amines.
- These polymers containing functional N-s ⁇ bstituted pyrroles may be employed as soft segments for block copolymers and crosslinked network polymers and as fuel additives and/or lubricating additives.
- fuel additives and/or lubricating additives For example, in a fuel composition or lubricating oil composition, such an additive is particularly useful as a detergent-dispersant.
- polyisobutyl N-substituted pyrroles prepared via carbocationic polymerization.
- Cationic polymerization involves carbenium ions and is essentially limited to those monomers with an electron releasing substituent such as alkoxy, phenyl, vinyl and 1,1-dialkyl; while anionic polymerization involves carbanions and requires monomers possessing electron withdrawing groups such as nitrile, carboxyl, phenyl and vinyl.
- carbenium ions are deficient by two electrons and are much less stable and therefore, controlled cationic polymerization requires specialized systems.
- the instability or high reactivity of the carbenium ions facilitates undesirable side reactions such as bimolceular chain transfer to monomer, ⁇ -proton elimination, and carbenium ion rearrangement, all of which limit the control over the cationic polymerization.
- low temperatures are necessary to suppress these reactions.
- cationic polymerization can display living characteristics. [0004] Through these living cationic systems, cationic polymerization can be controlled to yield tailored polymers with narrow molecular weight distributions and precisely controlled molecular weight, micro-architecture, and end group functionality.
- Controlled cationic polymerizations are deemed to be achieved under conditions in which chain end termination is reversible (quasiliving conditions) and undesirable reactions such as chain transfer and water-initiation are suppressed.
- a tremendous advantage of living and quasiliving polymerization is the opportunity for direct synthesis of telechelic polymers by one-pot in situ functionalization of the polymer by reaction of the living chain ends with an appropriate quenching reagent.
- telechelic polymer synthesis has often required one or more post- polymerization reactions to convert the chain ends to the desired functional group.
- Kennedy et al. Percec, V.; Guhaniyogi, S. C; Kennedy, J.P. Polym. Bull.
- Binder et al. (Machl, D.; Kunz, M.J.;Binder, W.H. ACSDiv. Polym. Chem., Polym. Preprs. 2003, 44(2). 858-859) quenched living polymerization of isobutylene with l-(3- bromopropyl)-4-(l -phenyivinyl)benzene, and then carried out a series of post- polymerization reactions on the product to obtain amine-terminated PIBs.
- the resulting end group structures were complex and bulky and very different from those disclosed herein, and the functionalization of the end groups was less than quantitative.
- polyisobutylene-based oil dispersants are typically produced by first polymerizing isobutylene (IB) to form an olefin-terminated polyisobutylene (PlB), reacting the PIB with maleic anhydride to form PTB-succinic anhydride (PIBSA), and then reacting PTBSA with a polyamine to form a PIB-succinimide amine.
- IB isobutylene
- PTBSA PTB-succinic anhydride
- the dispersant requires three synthetics steps; each stage requires separate reaction conditions and exhibits less than 100 % yield.
- Commercial implementation of in situ functionalization could reduce the time, energy, and overall cost associated with the production of oil and fuel additives.
- Living polymerization refers to any polymerization during which propagation proceeds with the exclusion of termination and chain transfer and thus yields polymers retaining (virtually indefinitely) their ability to add further monomer whenever it is supplied to the system.
- QLCCP quasiliving carbocationic polymerization
- chain end functionalization does not occur when these reagents are added to living polymerization of less reactive monomers such as isobutylene (see, e.g.: Ivan, B.; Kennedy, J.P. J. Polym. ScI: Part A: Polym. Chem. 1990, 28, 89-104; Fodor, Zs.; Hadjikyriacou, S.; Li, D.; Faust, R. . ACSDiv. Polym. Chem., Polym Preprs. 1994, 55(2), 492-493).
- monomers such as isobutylene
- Tert-chloride groups are not useful in nucleophilic substitution reactions, because the elimination product is usually obtained instead. Tert-chloride groups are also often undesirable as a dispersant/detergent for lubricants and fuels due to environmental reasons and since their presence may decrease the effectiveness of controlling soot and other engine contaminants. Additionally, tert-chloride groups tend to decompose, liberating HCl, which is corrosive toward metal surfaces within the engines.
- Faust et al. investigated 2-substituted f ⁇ ran derivatives and found that quantitative reaction with quasiliving PIB chain ends could be achieved in both titanium tetrachloride (TiCl 4 ) and BCl 3 co-initiated systems (Macromolecules 1999, 32, 6393, sadJ.Macromol., Sci PureAppl. Chem. 2000, A37, 1333.
- Ivan in WO 99/09074 disclosed quenching quasiiiving PIB with furan derivatives and thiophene derivatives while postulating that any aromatic ring, including 5-7 membered heterocycles as well as optionally substituted moieties could be employed to quench and effectively functionalize QLCP PIB through electrophilic aromatic substitution.
- aromatic ring, the substituent group on the ring, as well as the position of the substituent group on the ring there is particularity of the aromatic ring, the substituent group on the ring, as well as the position of the substituent group on the ring.
- the resulting telechelic polymers contain a tertiary nitrogen atom whose lone pair of electrons take part in the aromatic sextet of electrons in the 5-membered, aromatic pyrrole ring.
- the latter patent fails to disclose functional groups within the N-substituent of the N-subslituted pyrrole that are readily converted to functional groups containing basic nitrogen.
- Described herein are methods for producing telechelic polymers through cationic polymerization of a suitable monomer under living polymerization conditions and quenching the polymerization with an N-substituted pyrrole.
- the N-substituent contains a functional group that may be derivatized to basic amine.
- the methods described herein are directed to functionalization of a living or quasiliving polymer product by reacting and covalently bonding a functionaJized N-substituted pyrrole to the carbocationic propagating center.
- a functionalized N- substituted pyrrole employed as quenching agent to a living polymer or quasiliving polymer system can produce high amounts of monofunctional polymers having a single terminal N-substituted pyrrole group.
- bi- and multifunctional terminal N-substituted pyrrole groups can be formed depending on the functionality and micro-architecture of the living polymer. This method can be carried out with substantially no EAS coupling and, in some embodiments, less than 10 weight percent EAS coupling based upon total polymer produced.
- the N-substituent of the N- substituted pyrrole can be substituted with functional groups that do not complex with the catalyst system and are amenable to further reaction for the introduction of basic amine.
- R 1 and R 2 are, independently in each -(CR 1 R 2 )- unit, hydrogen or alkyj from
- m is an integer from 2 to 20;
- Z 1 is -F, -Cl, -Br, -I, -At, -CN, -NC, -N 3 , -NCO, -OCN, -NCS or -SCN;
- R' is a monovalent polyolef ⁇ n group; comprising a) ionizing a polyolef ⁇ n in the presence of a Lewis acid or mixture of Lewis acids to form a earbocation-terminated polyolef ⁇ n; b) reacting the earbocation-terminated polyolef ⁇ n from step (a) with an N- substituted pyrrole of formula II:
- R 1 and R 2 are selected so that the carbon adjacent to Z 1 has at least one hydrogen. In some embodiments, R 1 and R 2 are selected so that the carbon adjacent to Z 1 is a -CH 2 - group. In some embodiments, R 1 and R 2 in each -(CR 1 R 2 )- unit are hydrogen. In some embodiments, m is an integer from 2 to 6 and R 1 and R2 in each -(CR1R2)- unit are hydrogen.
- Z 1 is -F, -Cl, -Br, -I, -CN, -NC, -N 3 , -NCO, -OCN, -NCS or -SCN. In some embodiments, Z 1 is -Cl, -Br, -I, -CN, or -N 3 . In some embodiments, Z 1 is -Br, -CN, or -N 3 .
- the methods described herein can be used for the manufacture and synthesis of telechelic polymers with -F, -Cl, -Br, -I, -At, -CN, -NC, -N 3 , -NCO, -OCN, -NCS or -SCN attached to the polymer via an N-substiruted pyrrole linkage. Accordingly, another aspect of the methods provided herein is directed to the product produced by this method.
- This method can have a further step of contacting the resulting product formed above with a reagent or reagents in order to transform, displace, or react with, Z 1 in a manner such as to create compounds of formula III.
- R 1 and R 2 are, independently in each -(CR 1 R 2 )- unit, hydrogen or alkyl from
- R' is a monovalent polyolefm group; m is an integer from 2 to 20; and
- Z 2 is -NR 4 R 5 , ,-N[(R 4 )(COR 5 )], -N[(COR 4 )(COR 5 )], polyamino, polyamidoamino, polyaminoamido, -OR 6 , a polyether group, polyetheramino, or -COOR0; wherein R 4 and R 5 are each, independently, hydrogen, alkyl, or aryl; and R 6 is hydrogen, alkyl, aryl, alkaryl, or aralkyl.
- Z 1 can be displaced by a halide or pseudohalide prior to said further step.
- the reagent is a nucleophile, such as an amine, amide, imide, etc., in which case Z 1 is displaced to introduce a nitrogen group on the telechelic polymer.
- the reagent is a reducing agent which is capable of reducing Z 1 , such as -N3 or -CN to provide a basic nitrogen group on the telechelic polymer; for example, the reagent could be a hydrogenation agent used under reactive conditions.
- provided herein are the products produced according to the methods described herein, including the products produced according to the further step of contacting the resulting product formed above with the reagent or reagents.
- Suitable quasiliving polymer products having terminal tert-chloride chain end(s) can be pre-made by various methods. Tn some embodiments, these quasiliving polymer products can be made in situ, thus leading to one-pot functionalization reactions.
- the quasiliving polymer is formed by contacting at least one cationically polymerizable monomer with an initiator, in the presence of a Lewis acid and solvent under suitable quasiliving polymerization reaction conditions.
- Suitable cationically polymerizable monomers can be a single monomer, such that the quasiliving polymer product is a homopolymer; or selected from at least two cationically monomers, such that the quasiliving polymer product is a copolymer.
- At least one cationically polymerizable monomer is selected from the group consisting of isob ⁇ tylene, 2-methyl-1-butene, 3 -methyl- 1-butene, 4-methyl- 1-pentene, beta-pinene, isoprene, butadiene, and styrene, p-methylstyrene, vinyl toluene, ⁇ -methylstyrene, p-chlorostyrene, p-acetoxystryene, and similar styrenic monomers.
- the Lewis acid is TiCl 4 .
- the quasiliving polymer is then quenched with the N-substituted pyrrole of formula I after about 98 percent monomer conversion and prior to significant aging, which can lead to undesired side reactions.
- the initiator provides a suitable propagation center to begin the cationic polymerization.
- the initiator can be monofunctional, having one such propagation center, difunctional, having two propagation centers, or multifunctional, which can lead to the formation of star polymers.
- the initiator is monofunctional or difunctional.
- Monofunctional initiators include, but are not limited to, 2-chloro-2-phenylpropane; 2-acetoxy-2-phenylpropane; 2-propionyloxy-2-phenylpropane, 2-methoxy-2- phenylpropane, 2-ethoxy-2-phenylpropane, 2-ch3oro-2,4,4-trimethyl ⁇ entane, 2- acetoxy-2,4,4,-trimethylpentane, 2-propionyloxy-2,4,4-trimethylpentane, 2-methoxy- 2,4,4-trimethylpentane, 2-ethoxy-2,4,4-trimethylpentane, and functionally similar compounds.
- the monofunctional initiator is 2-cbloro-2,4,4- trimethylpentane. Tn some embodiments, the monofunctional initiator is 2-chloro- 2,4,4-trimethylpentane when a single monomer such as isobutylene is used.
- Difunctional initiators include, but are not limited to, 1 ,3-di( 1 -chloro- 1 -methylethyl)- 5- tert-butylbenzene, 1 ,3-di(l -acetoxy- 1 -methyletbyl)-5- tert-buty ⁇ benzene, 1 ,3-di(l - propionyloxy- 1 -methylethyl)-5- tert-butylbenzene, 1 ,3-di(l -methoxy- 1 -methylethyl)- 5- tert-butylbenzene, 1 ,3-di( 1 -ethoxy- 1 -methylethyl)-5-tert-butylbenzene, 1 ,4-di(l - chloro- 1 -methyjethyljbenzene, 1 ,4-di( 1 -acetoxy- 1 -methylethyl)benzene
- the difunctional initiator is 1,3-di(l -chloro- l-methylethyl)-5-tert-butylbenzene or 2,6-dichloro-2,4,4,6- tetramethylbeptane. In some embodiments, the difunctional initiator is l ,3-di(l- chloro-1 -methylethyl)-5-tert-butylbenzene or 2,6-dichloro-2,4,4,6-tetramethylheptane when a single monomer such as isobutylene is used.
- a class of products produced in accordance with the methods disclosed herein can be characterized by having a narrow molecular weight distribution Mw/Mn of less than 1.5, or, in other embodiments less, than about 1.2.
- the method described above can be used for the manufacture and synthesis of telechelic polymers with terminal groups containing basic nitrogen or oxygen attached to the polymer via an N-substituted pyrrole linkage. Accordingly, provided herein are the products produced by the methods described herein.
- provided herein are compounds of formula IV:
- R 1 and R?. are, independently in each -(CR 1 R 2 )- unit, hydrogen or alkyl from
- R' is a monovalent polyolefin group; m is an integer from 2 to 20; and
- Z 3 is Z 1 or Z 2 as defined above.
- R 1 and R 2 of formula IV are selected so that the carbon adjacent to Z 3 has at least one hydrogen, In some embodiments, R 1 and R 2 of formula IV are selected so that the carbon adjacent to Z 3 is a -CH 2 - group. In some embodiments, R 1 and R 2 in each -(CR 1 R 2 )- unit are hydrogen. In some embodiments, m is an integer from 2 to 4 and R 1 and R 2 in each -(CR 1 R 2 )- unit are hydrogen. [0021] In some embodiments, n is an integer from about 2 to 1000. In some embodiments, n is 3 to 500. In some embodiments, n is 4 to 260.
- compounds for use in fuel additives are when n is from 4 to about 20 and for as dispersants and lubricating additives when n is from 6 to about 50 and when used as a viscosity index improver then n is typically from 140 to about 260.
- Z 3 is Br, CN, and N3; or NR 4 R5, wherein R 4 and R5 are independently selected from the group of hydrogen, alkyl, aryl, alkaryl, aralkyl; and OR-6, wherein R 6 is selected from the group of hydrogen, alkyl, aryl, alkaryi, aralkyl; and polyamino.
- R 1 and R 2 are, independently in each -(CR 1 R 2 )- unit, hydrogen or alkyl from
- R 3 is a monofunctional or poly functional carbocationic initiator residue of functionality r, where r can vary from 1 to 8:
- R" is a divalent polyoief ⁇ n group; m is an integer from 2 to 20; and
- Z 3 is Z 1 or Z 2 as defined above.
- R 1 and R 2 are selected so that the carbon adjacent to Z 3 has at least one hydrogen, In some embodiments, R 1 and R 2 are selected so that the carbon adjacent to Z 3 is a -CH 2 - group. Tn some embodiments, R 1 and R 2 in each - (CR 1 R 2 )- unit are hydrogen. In some embodiments, m is an integer from 2 to 4 and R 1 and R 2 in each -(CR 1 R 2 )- unit are hydrogen.
- n is independently, in each of the r chain segments, an integer from about 1 to 1000. In some embodiments, n is independently, in each of the r chain segments, an integer from 2 to 500. In some embodiments, n is independently, in each of the r chain segments, an integer from 2 to 100.
- Z 3 is Br, CN, N3; or NR 4 R 5 , wherein R 4 and R5 are independently hydrogen, alkyl, aryl, aJkaryl, aralkyl; or OR 6 , wherein R 6 is selected from the group of hydrogen, alkyl, aryl, alkaryl, and aralkyl.
- the polyisobutyl N-substituted pyrrole compounds of formula IV and formula V are typically mixtures having the PIB group attached to the N-substituted pyrrole at the 2 and/or 3 position of the pyrrole.
- the presence of Z 1 within the substituent group on the N-substituted pyrrole directs the product distribution toward a preponderance of the 3 isomer.
- the relative preponderance of the 3 isomer compared to the 2 isomer depends upon the reaction conditions as well as the identity of the Z 1 and its location within the s ⁇ bstituent on the 1 position of the pyrrole. In some embodiments, the fraction of 3 isomer is 0.65 or higher.
- the fraction of 3 isomer is 0.7 or higher.
- suitable separation technologies such as chromatography, zone electrophoresis and the like can be employed to further refine the product. Accordingly, substantially 3- polyisobutyl N- substituted pyrrole can be formed.
- substantially in some embodiments, refers to having greater than 75% of the specified isomer or, in other embodiments, greater than 90%.
- FIG. 1 shows the 1 H NMR spectrum of myofunctional PIB carrying primary chloride end groups prepared by quenching quasiliving PIB with l-(2- chloroethyl)pyrrole.
- the product is a mixture of major and minor isomers with PIB in the 3- and 2-positions of the pyrrole ring, respectively.
- Expansion of the 1.6-2.1 region shows complete consumption of tert-chlo ⁇ de end groups as indicated by the absence of characteristic peaks at 1.96 and 1.68 ppm.
- FIG. 2 shows the 13 C N_ MR spectrum of monofunctional PIB carrying primary chloride end groups prepared by quenching quasiliving PIB with l-(2- chloroethyl)pyrrole.
- the product is a mixture of major and minor isomers with PIB in the 3- and 2-positions of the pyrrole ring, respectively.
- FlG. 3 shows partial_ 1 H NMR spectra of the reaction product of quasiliving PTB with 1 -(2-chloroethyl)pyrrole, as a function of time.
- FIG. 4 shows GPC traces of PIB before (dotted) and after (solid) reaction with l-(2-chloroethyl)pyrrole.
- FIG. 5 shows the 1 H NMR spectrum of monofunctional PIB carrying primary bromide end groups prepared by quenching quasiliving PIB with l-(2- bromoethyl)pyrrole.
- the product is a mixture of major and minor isomers with PIB in the 3- and 2-positions of the pyrrole ring, respectively.
- Expansion of the 1.6-2.1 region shows the complete consumption of tert-cbloride end groups as indicated by the absence of characteristic peaks at 1.96 and i .68 ppm.
- FIG. 6 shows the 13 C NMR spectrum of monofunctional PIB carrying primary bromide end groups prepared by quenching quasiliving PIB with 1 -(2- bromoethyl)pyrrole.
- the product is a mixture of major and minor isomers with PIB in the 3- and 2-positions of the pyrrole ring, respectively.
- FIG. 7 shows partial 1 H NMR spectra of the reaction product of quasiliving PIB with l-(2-bromoethyl)pyrrole, as a function of time.
- FIG. 8 shows GPC traces of PIB before (dotted) and after (solid) reaction with l-(2-bromoethyl)pyrrole.
- FlG. 9 shows the H NMR spectrum of difunctionai PIB carrying primary chloride end groups prepared by quenching quasiliving PIB with l-(2- chloroethyl)pyrrole.
- the end groups are a mixture of major and minor isomers with
- 2.2 region shows the complete consumption of tert-chloride end groups as indicated by the absence of characteristic peaks at 1.96 and 1.68 ppm.
- FIG. 10 shows the GPC trace of difunctionai PIB after reaction with 1 -(2- ch3oroethyj)pyrrole.
- FIG. 11 shows the 1 H NMR spectrum of difunctionai PIB carrying primary bromide end groups prepared by quenching quasiliving PIB with l-(2- bromocthyl)pyrrole.
- the end groups are a mixture of major and minor isomers with
- 2.2 region shows the complete consumption of tert-chloride end groups as indicated by the absence of characteristic peaks at 1.96 and 1.68 ppm.
- FlG. 12 shows the GPC trace of difunctionai PIB after reaction with 1 -(2- bromoethyl)pyrrole.
- FIG. 13 shows partial 1 H NMR spectra of the reaction product of monofunctional quasiliving PIB with l-(3-bromopropyl)pyrrole, as a function of time.
- FIG. 14 shows the 1 H NMR spectrum of difunctionai PIB carrying primary bromide end groups prepared by quenching quasiliving PIB with l-(3- bromopropyl)pyrrole.
- the product is a mixture of major and minor isomers with PIB in the 3- and 2-positions of the pyrrole ring, respectively.
- FIG. 15 shows partial 1 H NMR spectra of the reaction product of difunctionai quasiliving PIB with l-(3-bromopropyl)pyrrole, as a function of time.
- FIG. 16 shows the 1 H NMR spectrum of monofunctional 1 -(2- azidoethyl)pyrrole-PlB (mixed 2- and 3-isomers) obtained by post-polymerization replacement of chloride by azide ion.
- FIG. 17 shows partial 1 H NMR spectra of the reaction product of monofunctional quasiliving PIB with l-(2-cyanoethyl)pyrrole, as a function of time.
- FIG. 18 shows the 1 H NMR spectrum of monofunctional PlB carrying primary cyanide end groups prepared by quenching quasiliving PIB with l-(2- cyanoethyl)pyrrole.
- the product is a mixture of major and minor isomers with PIB in the 3- and 2-positions of the pyrrole ring, respectively.
- FIG. 19 shows partial 1 H NMR spectra of the reaction product of difunctional quasiJiving PlB with l-(2-cyanocthyl)pyrrole, as a function of time
- FIG. 20 shows GPC traces of difunctional PIB before (dotted) and after (solid) reaction with l-(2-cyanoethyl)pyrrole.
- FIG. 21 shows the 1 H NMR spectrum of difunctional PlB carrying primary cyanide end groups prepared by reaction of tert-chloride-terminated PIB with l-(2-azidoethyl)pyrrole in the presence of TiCl 4 .
- the product is a mixture of major and minor isomers with PIB in the 3- and 2-positions of the pyrrole ring, respectively.
- FIG. 22 shows GPC traces of difunctional PlB before (dotted) and after (solid) reaction with l-(2-azidoethyl)pyrrole.
- telechelic polymer refers to polymers having one or more end groups wherein the end group has the capacity to react with another molecule or perform a specific function. Polymers having one reactive end group per molecule are said to be monofunctional. Polymers having two reactive chain ends per molecule are said to be difunctional. Polymers having more than two reactive chain ends per molecule are said to be multifunctional.
- alkyl refers to a uni-valent, saturated hydrocarbon chain or group of about 1 to about 20 carbons.
- the alkyl group contains about 1 to about 15 carbons.
- the alkyl group contains about 1 to about 10 carbons.
- the alkyl group contains about 1 to about 8 carbons.
- the alkyj group contains about 1 to about 6 carbons.
- the alkyl group contains about 1 to about 3 carbons.
- the alkyl group contains 1 to 2 carbons.
- the alkyl group is primary. In some embodiments, the alkyl group is secondary.
- the alkyi group is tertiary.
- the alkyl is methyl, ethyl, n-propyl, isopropyl, isobutyl, n-butyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, or isohexyl.
- the alkyl is methyl, ethyl, n-propyl, or isopropyl.
- the alkyl is methyl.
- the alkyl is tert-butyl.
- the aikyl group is a straight hydrocarbon chain.
- the alkyl group is a branched hydrocarbon chain. In some embodiments, the alkyl group is cyclic.
- alkoxy refers to the group aikyl-O. Alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, tert- butoxy, sec-butoxy, n-pentoxy, n-hexoxy, 1,2-dimethylbutoxy, and the like.
- alkenyl refers to a monovalent branched or unbranched unsaturated hydrocarbon group having, in some embodiments, from 2 to 20 carbon atoms.
- the alkenyl group has 2 to about 10 carbon atoms. In other embodiments, the alkenyl group has 2 to 6 carbon atoms. Is some embodiments, the alkenyl group has at least 1, and in other embodiments, from 1 -2 sites of vinyl unsaturation. Tn some embodiments, the alkenyl group is ethenyl (-CH-CII 2 ), n-propenyl (-CII 2 CH-CII 2 ), iso-propenyl (-C(CH 3 ) -CH 2 ), or the like. [0056] As used herein, "aryl” refers to a univalent monocyclic or multicyclic aromatic group containing from 6 to about 30 carbons.
- the aryl is monocyclic. In some embodiments, the aryl contains about 6 to about 15 carbons. In some embodiments, the aryl contains about 6 to about 10 carbons. In some embodiments, the aryl is fluorenyl, phenyl, naphthyl or anthyl. In some embodiments, the aryl is phenyl. Tn some embodiments, the aryl is substituted.
- aryl groups can optionally be substituted with from 1 to 5 s ⁇ bstituents, or, in some embodiments, 1 to 3 substituents selected from the group consisting of alkyl, alkoxy, acyl, alkylsulfanyl, alkylsufonyl, alkyl sulfenyl, alkylcarbonyl, alkyoxycarbonyl, aminocarbonyl, aminocarbonylamino, halo, cyano, nitro, and the like.
- EAS coupling refers to ring alkyjation of a single N- substituted pyrrole by two carbocation-terminated polyolefin chains.
- heteroaryl refers to a univalent monocyclic or multicyclic aromatic group containing from 5 to 15 carbon atoms and 1 to 4 heteroatoms selected from oxygen, nitrogen, and sulfur within at least one ring. In some embodiments, the heteroaryl contains 5 to about 10 ring atoms. In some embodiments, the heteroaryl contains 5 or 6 ring atoms. In some embodiments, the heteroaryl is monocyclic. In some embodiments, the heteroatom is N, O, or S.
- the heteroaryj contains one heteroatom. In some embodiments, the heteroaryl contains 1 to 3 N atoms. In some embodiments, the heteroaryl contains one O or S atom and one or two N atoms.
- heteroaryl used herein include, but are not limited to, f ⁇ ran, thiophene, pyrrole, imidazole, pyrazole, triazole, tetrazole, thiazoie, oxazole, isooxazole, oxadiazole, thiadiazole isothiazole, pyridine, pyridazine, pyrazine, pyrrolidine, quinoline, isoquinoline, benzofuran, benzothiophene, indole, indazole, and the like.
- halide refers to a univalent fluoride, chloride, bromide, iodide, or astatide radical.
- polyolef ⁇ n group refers to a polyolef ⁇ n substituent.
- the polyolef ⁇ n group is a poiyisobutyl group or a poiyisobutylene group.
- isobutylene refers to isobutene. Also as used herein,
- polyisob ⁇ tene refers to polyisob ⁇ tene.
- poiyisobutyl group refers to a monovalent polyolef ⁇ n group comprising at least 2 isobutylene monomer units. Tn some embodiments, the poiyisobutyl group is wherein R is H or alkyj of 1 to about 10 carbons, and n is an integer from about 10 to about 2000. In further embodiments, n is about 10 to about 1000. In further embodiments, n is about 10 to about 500. In further embodiments, n is about 10 to about 250. In further embodiments, n is about 10 to about 100. In further embodiments, n is about 10 to about 50. [0064] As used herein, “polyisobutylene group” refers to a divalent polyolefin group comprising at least 2 isobutylene monomer units. In some embodiments, the polyisobutylene group is
- n is an integer from about 10 to about 2000. In further embodiments, n is about 10 to about 1000. In further embodiments, n is about 10 to about 500. Tn further embodiments, n is about 10 to about 250. In further embodiments, n is about 10 to about 100. In further embodiments, n is about 10 to about 50. [0065] In some embodiments, provided herein are methods for preparing a telechelic polymer of the formula I:
- R 1 and R 2 are. independently in each -(CR 1 R 2 )- unit, hydrogen or alkyl from 1 to 6 carbon atoms; m is an integer from 2 to 20; Z 1 is -F, -Cl, -Br, -I, -At, -CN, -NC, -N 3 , -NCO, -OCN, -NCS or -SCN; and
- R is a monovalent polyolefm group; comprising: a) ionizing a polyolefm in the presence of a Lewis acid or mixture of Lewis acids to form a carbocation-terminated polyolefin; b) reacting the carbocation-terminated polyolefin from step (a) with an N- substituted pyrrole of formula II:
- At least one of R 1 or R 2 of the -C(CR 1 R) 2 - group adjacent to Z 1 is hydrogen.
- the -(CR 1 R 2 )- group adjacent to Z 1 is a -CH 2 -.
- R 1 and R 2 are both hydrogen.
- m is 2-6.
- m is 2-4.
- m is 2-3.
- Tn some embodiments, m is 2.
- Zj is -F, -Cl, -Br, -I, -CN, -NC, -N 3 , -NCO, -OCN, -NCS, or -SCN.
- Zj is -Cl, -Br, -I, -CN, or -N 3 .
- Z 1 is -Cl, -Br, -CN, or -Nj.
- Zj is -Br, -CN, or -N3. Tn some embodiments, Z 1 is -C3 or -Br. In some embodiments, Z 1 is -Br.
- m is 2-6 and R 1 and R 2 are both hydrogen.
- m is 2-4: Z 1 is -Cl, -Br, -CN, or -N 3 ; and R 1 and R 2 are both hydrogen.
- the N-substituted pyrrole of formula II is
- the telechelic polymer of formula I is
- the telechelic polymer of formula 1 is
- R is a polyisobutyl group.
- the telechelic polymer of fonnuia T is
- R" is a divalent polyolefin group and R 3 is a monofimctional or polyfimctional carbocationic initiator residue of functionality r, wherein r is an integer from 1 to 8.
- the telechelic polymer of formula 1 is
- the telechelic polymer of formula I is
- the telechelic polymer of formula I is
- R" is a polyisobutylene group.
- r is 2-3.
- r is 2.
- R3 is , wherein R x is H or alkyl. In some embodiments, R x is tert-butyl.
- R 3 is
- R? is
- R 3 is
- Living polymerization is known in the art and may be achieved using a variety of systems, some of which are described in U.S. Pat. Nos. 5,350,819; 5,169,914; and 4,910,321.
- living carbocationic polymerization systems can comprise ideal living polymerization, based on cationic initiation in which the rates of chain transfer and termination are zero or indistinguishable from zero, and quasiliving polymerization in which reversible termination is operable, but the rates of chain transfer and irreversible termination are zero or indistinguishable from zero.
- Suitable systems disclosed in the art for living carbocationic polymerization are for instance: tert-aJkyl halides (or ethers or esters)/BCl 3 ; tert-alkyl halides (or ethers or esters)/TiCl 4 ; cumyl halides (or ethers or esters)/BCl 3 ; cumyl halides (or ethers or esters)/TiCl 4 ; tert-alkyl halides/BCl 3 /2,6-dimethylpyridine (2,6- DMP) (or 2,4-dimethylpy ⁇ dine or 2,6-di-tert-buty3pyridine); tert-alkyl halides/TiCl4/2,6-DMP (or 2,4-DMP or 2,6-di-tert-butylpyridine); cumyl halide/BCl 3 /2,6-DMP (or 2,4-DMP or 2,6-di-ter
- the suitable systems are hexane/MeC1/TiCl 4 /2,6- DMP/-70 °C; MeCl/BCl 3 /2,6-DMP/-40 °C; 1,2-EtCl 2 /BCl 3 /2,6-DMP/-10 °C.
- the suitable systems are those systems employing isobutylene as the monomer and that are initiated with 2-chloro-2,4,4-trimethylpentane (TMPCl) or by 5-tert-butyl-1,3,-di(l-chloro-1-methylethyl)benzene (bDCC) or 2,6-dichloro-2,4,4,6- tetramethylheptane.
- An important aspect to quasiliving cationic polymerization is the use of a reaction system in which the propagating centers are of sufficiently low reactivity so that transfer and termination reactions are suppressed but not so unreactive that propagation by a suitable cationic monomer is suppressed. This is facilitated by appropriately matching the stability of the carbocationic center with a suitable counterion complex, solvent polarity, polymerization temperature, other additives, etc.
- an initiator comprising a tertiary alkyl halide, a tertiary aralkyl halide, a tertiary alkyl ether, a tertiary aralkyl ether, a tertiary alkyl ester, a tertiary aralkyl ester, or the like;
- Lewis acid co-initiator which typically comprises a halide of titanium, boron, tin, or aluminum;
- Initiator compounds for living carbocationic polymerization are known in the art.
- the type of contemplated initiator compounds can be represented by the general fonnuia (X-CR a Rb) r -Rc wherein R a and R b are univalent radicals independently selected from the group consisting of hydrogen, alkyl, aryl, aralkyl or alkaryl groups, and can be the same or different, and X is acyloxy, alkoxy, hydroxy, or halogen.
- R a and Rb are both methyl.
- R c is an aliphatic or aromatic polyvalent radical with valance r, where r is an integer of 1 to 8.
- R a , R b , and R c are hydrocarbon groups containing 1 to 20 carbon atoms. In some embodiments, Ra, Rb, and Rc are hydrocarbon groups containing 1 to 8 carbons atoms. In some embodiments, X is a halogen, In further embodiments, X is chloride. In some embodiments, R 1 : is aryl or alkaryl. In some embodiments, R c is 1 ,4-phenylene. In some embodiments, Rc is 5-tert-butyl-1,3-phenylene. In some embodiments, R c is neopentylene.
- R c is a trivalent benzene ring with the (X-CRaRb) groups attached at the 1, 3, and 5 positions of the ring.
- the structure of R a , R b , and R c is selected to mimic the growing species derived from the monomer, e.g., a i-phenylethyl derivative for polystyrene or 2,4,4-trimethylpentyl derivative for poiyisobutylene.
- Suitable compounds include, for example, but are not limited to, 2-chloro-2-phenylpro ⁇ ane; 2-acetoxy-2- phenylpropane; 2-propionyloxy-2-phenylpropane, 2-methoxy-2-phenylpropane, 2- ethoxy-2-phenylpropane, 2-chloro-2,4,4-trimethylpentane, 2-acetoxy-2,4,4,- trimethylpentane, 2-propionyloxy-2,4,4-trimethylpentane, 2-methoxy-2,4,4- trimethylpentane, 2-e ⁇ hoxy-2,4,4-trimethylpentane, 1 ,3-di(l-chloro-1-methylethyl)-5- tert-butylbenzene, 1,3-di(l-acetoxy-1-methylethyl)-5- tert-butylbenzene, 1,3-di(l- propionyloxy- 1 -methy le
- the initiator is 2-chloro-2,4,4-trimethylpentane (TMPCl), 1,4- di(l -chloro-1-methylethyl)benzene (DCC),1,3,5 tri(l-chloro-1-methyletbyl)benzene (TCC), 1,3-di(l -chloro-1-methylethyl)-5-tert-butylbenzene (bDCC), or 2,6-dichloro- 2,4,4,6-tetramethylheptane.
- TMPCl 2-chloro-2,4,4-trimethylpentane
- DCC 1,4- di(l -chloro-1-methylethyl)benzene
- TCC 1,3,5 tri(l-chloro-1-methyletbyl)benzene
- bDCC 1,3-di(l -chloro-1-methylethyl)-5-tert-butylbenzene
- carbocationic initiator residue refers to the polyvalent radical (-CR a R b ) r -R c , where r, R a , R b , and R c are defined above.
- r the carbocationic initiator residue is a "monovalent or univalent carbocationic initiator residue.”
- r is greater than 1, the carbocationic residue is a ''polyvalent or multivalent carbocationic initiator residue.”
- Lewis acids are suitable as catalysts for purposes of the methods described herein. In some instances these Lewis acids are also referred to as co- initiators, and both terms are used herein. Such compounds include, but are not limited to the titanium and boron halides, Tn some embodiments, the Lewis acid is titanium tetrachloride, boron trichloride, aluminum trichloride, tin tetrachloride, zinc dichloride, ethyl aluminum dichloride, or others. In some embodiments, the Lewis acid is a titanium haiide. In further embodiments, the Lewis acid is titanium tetrachloride. Tn some embodiments, the strength of the Lewis acid and its concentration should be adjusted for the particular monomer.
- Lewis acids such as TiCLt, BCJ3, or SnCl 4 are used.
- vinyl ethers can be polymerized using iodine or zinc halides.
- the Lewis acid is selected to comprise labile Hgands such that it does not contain exclusively strongly bonded ligands such as fluoride. Additionally, the strength of these Lewis acids can be adjusted using nucleophilic additives.
- the amount of the Lewis acid present in the initiator system may vary. In some embodiments, the concentration of Lewis acid exceeds the electron donor or salt concentration present. The Lewis acid concentration should not be so high as to precipitate the formed polymer, e.g., PTB.
- an electron donor, proton trap, proton scavenger, common ion salt, and/or common ion salt precursor may be optionally present during production of the polymer.
- These additives have been shown to convert traditional polymerization systems into living and/or quasiliving cationic polymerizations systems; whereby polymers having controlled structures with narrow molecular weight distribution are produced.
- the electron donor optionally used herein is not specifically limited to any particular compound or class of compounds, and examples thereof include, but are not limited to pyridines and «-alkyl amines, aprotic amides, sulfoxides, esters, metal compounds having an oxygen atom bonded to a metal atom, and others.
- pyridine compounds such as 2,6-di-tert-butylpyridine (DtBP), 2,6-dimethylpyridine (2,6-DMP), 2,4-dimethylpryidine (2,4-DMP), 2,4.6- trimethylpyridine, 2-methylpyridine, pyridine; N,N-dimethylaniline; amide compounds such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N- diethylacetamide; sulfoxide compounds such as dimethyl sulfoxide; ether compounds such as diethyl ether; ester compounds such as methyl acetate, ethyl acetate; phosphate compounds such as trimethyl phosphate, tributyl phosphate, triamide hexamethylphosphate; and oxygen-containing metal compounds such as tetraisopropyl titanate.
- DtBP 2,6-di-tert-butylpyridine
- 2,6-DMP 2,6-dimethylpyridine
- a proton scavenger is defined in U.S. Pat. No. 5,350,819. Electron donors have been defined in EPA 341 012. Both of these documents are incorporated by reference herein.
- Common ion salts and/or common ion salt precursors optionally may be added into the living charge. Typically, these salts are used to increase the ionic strength, suppress free ions, and beneficially interact with ligand exchange.
- the common ion salt precursor is a quaternary ammonium salt, such as W-Bu 4 NCl.
- Other suitable salts are disclosed in U.S. Pat. No.
- Such polymers can be low molecular weight liquid or viscous polymers having a molecular weight of from about two hundred to ten thousand g/mol, or solid waxy to plastic, or elastomeric materials having molecular weights of from about ten thousand to one hundred thousand g/mol, or more.
- Suitable monomeric materials include such compounds as isobutylene, styrene, beta-pinene, isoprene, butadiene, substituted compounds of the preceding types, and others. Tn some embodiments, the monomer is isobutylene, 2-methyl-butene, 3-methyl-1- butene, 4-methyl-1-pentene, beta-pinene, or styrene.
- the monomer is isobutylene. Mixtures of monomers may be used.
- Solvents influence the ionization equilbria and rates of exchange of growing species through their polarity, which can be estimated from their dielectric constants. In some embodiments, solvents having low dielectric constants are used because the ion pairs are Jess dissociated. Suitable solvents include, but are not limited to, low-boiling alkanes and alkyl mono or polyhalides with reasonably low freezing points to be used at polymerization temperature.
- Illustrative solvents include, but are not limited to, aikanes (generally C 2 to Cio alkanes, including normal alkanes such as propane, normal butane, normal pentane, normal hexane, normal heptane, no ⁇ nal octane, normal nonane and normal decane, and branched alkanes including isobutane, isopentane, isohexane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane and the like), alkenes and alkenyl halides (such as vinyl chloride), carbon disulfide, chloroform, eihyichloride, n-butyl chloride, methylene chloride, methyl chloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, sulfur dioxide, acetic anhydride, carbon tetrachloride, acetonitriJe,
- the polymerization medium is substantially free of substances that are capable of initiating the monomers other than the purposefully- added initiator (or mixture of initiators) employed in the methods described herein.
- the polymerization medium is substantially free of unwanted cationic polymerization initiators or promoters (i.e., adventitious initiators) such as water, alcohols, carboxylic acids and acid anhydrides, Bronsted acids, ethers, or mixtures thereof.
- the alcohols which should be excluded are straight or branched chain, aliphatic, aromatic, or mixed aliphatic/aromatic alcohols containing from 1 to 30 carbon atoms.
- carboxylic acid, acid anhydride and/or ether initiators to be excluded are halide substituted or unsubstituted, straight or branched chain, aliphatic, aromatic or mixed aliphatic/aromatic acids and ethers containing from about 1 to about 30 carbon atoms.
- the polymerization reaction medium contains Jess than about 20 weight ppm (part per million) of water, and less than 5 weight ppm of mercaptans, both of which can function as poisons to Lewis Acid catalysts and/or as adventitious initiators.
- the olefin feed can be treated to achieve the above desired levels by conventional means, e.g., by use of mole sieves and caustic washing to reduce the concentration of mercaptans and water, and remove dienes (if desired).
- the polymerization reaction may be conducted batchwise or as a semicontinuous or continuous operation in which continuous streams of ingredients are delivered to the reactor; appropriate reactor systems include but are not limited to continuously stirred tank reactor systems, wherein an overflow of a slurry or solution of polymer is taken out for the recovery of the polymer therefrom, or plug flow reactors, ]n some embodiments, the reactor contents are stirred or agitated to achieve an even catalyst distribution therein.
- the mode of reaction is a batch process; although theoretically a plug flow reactor may have process advantages.
- the molecular weight of the polymer can be manipulated by varying the ratio of the concentrations of the monomer to the initiator as in most living polymerizations. See for example U.S. Pat. Nos. 5,350,819; 5,169,914; and 4,910,321, which are incorporated by reference herein. Control of the polymer molecular weight within defined limits of a selected target polymer molecular weight is particularly important when the polymer is intended for use in lubricating oils as a dispersant.
- the catalyst amount affects the rate of conversion of the olefin monomer and hence the yield of polymer as a function of reaction time; higher amounts of Lewis acid catalyst typically yield faster conversions and higher yields. Strong Lewis acid catalyst in the absence of an electron donor species can lead to isomerizations which reduce the functionality of the polymer, and can produce undesirable chain transfer.
- the catalyst should be employed in sufficient amount to enable the reaction to proceed at a reasonable rate and in a controlled manner.
- the catalyst concentration corresponds to about the quantitative formation of complex between the catalyst and the initiator compound.
- the catalyst is employed at a ratio of moles of Lewis acid to equivalents of functional groups on the initiator of more than 3:1. In some embodiments, the ratio is more than 4:1. In other embodiments, the ratio is more than 6: 1. In some embodiments, the range of ratio is from 3:1 to 30:1. In other embodiments, the range of ratio is 4:1 to 20:1. In further embodiments, the range of ratio is 6:1 to 10:1.
- BCI3 Lewis acid When isobutylene is the monomer, BCI3 Lewis acid typically yields relatively slow propagation rates and relatively slow quenching rates compared to TiCl 4 Lewis acid. This is attributed to a lower ionization equilibrium in a BCI3 system, which yields lower concentrations of reactive carbenium ions available for reaction with a functionalized N-substituted pyrrole of the methods described herein employed as a quenching agent. Using a TiCl 4 catalyst promotes faster propagation rates and more rapid quenching rates due to the larger ionization equilibrium associated with this system.
- the temperature at which the polymerizations are carried out is important, since higher temperatures tend to decrease the functionalization degree. Additionally, depending upon the living or quasiliving system, too high a reaction temperature can diminish or eliminate the living character of the cationic polymerization.
- the usual polymerization temperature range is between about -100 °C and +10 °C.
- the polymerizations are performed at a temperature at or below -10 °C. In some embodiments, the temperature is at or below -30 °C. In some embodiments, the temperature is between about -80 °C and about -50 °C. In some embodiments, the temperature is about -60 °C.
- the liquid-phase reaction mixture temperature is controlled by conventional means.
- Average polymerization times can vary from about 2 to about 1000 minutes, In some embodiments, the polymerization time is from about 5 to about 120 minutes. In some embodiments, the polymerization time is from about 10 to about 60 minutes. In some embodiments, the polymerization time is from about 20 to about 30 minutes. In some embodiments, polymerization is carried out for a time suitable to allow for monomer conversion above 80 %. ]n other embodiments, polymerization is carried out for a time suitable to allow for monomer conversion above 90?/o. In some embodiments, polymerization is carried out for a time suitable to allow for monomer conversion above 98 %.
- polymerization is carried out for a time suitable to allow for essentially quantitative monomer conversion, but not so long that substantial aging occurs, characterized by the occurrence of chain end isomerization, proton elimination, or other termination or deactivation events, prior to quenching the living carbocationic polymerization to end cap and thus functionaiize the resulting polymer with an N-substituted pyrrole.
- Other methods may be used to prepare other pre-made polymers, which are also suitable for functionalization with the N-substituted pyrroles described herein.
- Suitable pre-made polymers are those made by an inifer technique (described below), from terminated living and quasiliving polymerization products, by conventional polymerizations followed by an extra hydro-chlorination step, or by other polymerization techniques so long that the end result is a polymer backbone having chain ends, such as tert-chloride, that can be ionized with a suitable Lewis acid catalyst, and thus suitably functionalized with the N-substituted pyrroles described herein.
- Methods to obtain polymers having a terminal tertiary halide group include use of a system of initiator-transfer agents, called inifers (from initiator- transfer functions).
- These pre-made terminally halogenaied polymers may be thought of as a substitute for the initiator and monomer present in a living polymerization system and are treated as equivalent, in terms of end group functionality, to the polymers prepared by the living polymerization of the monomer.
- these halogenated polymers are added to the catalyst system by dissolving the polymer in a solvent of choice, much the same way that monomer and initiator are added to a living polymerization charge.
- the stoichiometry of the catalyst ingredients is calculated assuming that the pre-made polymer is a substitute for the initiator, i.e. one halide terminus is equal to one initiator site.
- the functionalized N -substituted pyrrole quenching agent is added, followed by the Lewis acid.
- the Lewis acid is added, followed by the functionalized N-substituted pyrrole quenching agent.
- the functionalized N-substituted pyrrole quenching agent and Lewis acid are added simultaneously.
- the functionalized N-substituted pyrrole quenching agent and/or the Lewis acid may be first dissolved in a solvent or mixture of solvents before addition to the reaction. Functionalization proceeds according to the method described herein.
- Suitable functionalized N-substituted pyrroles for end capping the teti- chloride chain end of the quasiliving carbocation polymer are said to be "soft" nucleophiles, which means they are amenable to electrophilic aromatic substitution (EAS) by the quasiliving polymer carbocation but not sufficiently nucleophilic to complex with or decompose the Lewis acid.
- the functionalized N-substituted pyrroles are substituted with a component that is less nucleophilic than the pyrrole and which does not deactivate the catalyst complex.
- the lone pair of electrons on the pyrrole nitrogen atom takes part in the aromatic sextet of electrons in the five-membered aromatic pyrrole ring. This structure dramatically reduces the complexation of nitrogen with the Lewis acids and increases the nucleophilic character of the aromatic ring, thus creating a soft nucleophile which is highly reactive with carbenium ions.
- the functionalized N-substituted pyrroles substantially undergo only mono-substitution, Le., after the functionalized N- substituted pyrrole quenching agent has undergone ring-substitution with one quasiliving carbocationic polymer, it does not undergo a second substitution.
- a second substitution onto the functionalized N-substituted pyrrole is referred to as "EAS coupling.'"
- the N-substituted pyrrole is a compound of formula TI, wherein: R 1 and R? are, independently in each -(CR 1 R?)- unit, hydrogen and alkyl from 1 to 6 carbon atoms; m is an integer from 2 to 20; and Z 1 is -F, -Cl, -Br, -I, -At, -CN, -NC, -N 3 , -NCO, -OCN, -NCS or -SCN. [00109] In some embodiments, Z t is -F, -Cl, -Br, -1, -CN, -NC, -N ? , -NCO, -OCN, -NCS or -SCN.
- Patent Application 2006/0041081 Al discloses that quenching of quasiliving PIB with 2,5-disubstituted pyrroles yields predominantly ex ⁇ -olefin PlB. jOOlllJ
- the chemistry of preparing the suitable functionalized N-substituted pyrrole compounds for use in the methods described herein is well known in the art; see for example, The Synthesis, Reactivity, and Physical Properties of Substituted Pyrroles. Volume 48, Part 1-2, John Wiley and Sons (1992) incorporated herein by reference in its entirety. Often a desired functionalized N-substituted pyrrole may be readily prepared from a different precursor N-substituted pyrrole by simple nucleophilic substitution.
- an N-(bromoalkyl)pyrrole may be reacted under appropriate conditions with sodium azide in order to displace the bromide group and replace it with an azide group.
- N- substituted pyrroles that are functionalized within the N-substituent and can be suitably employed include, but are not limited to: N-(haloalkyl)pyrroles, e.g., N-(2- fluoroethyl)pyrrole, N-(3-fluoropropyl)pyrrole, N-(4-fluorobutyl)pyrrole, N-(6- fluorohexyl)pyrrole, N-(8-fluorooctyl)pyrrole, N-(2-fiuoro-1-propyl)pyrrole, N-(I- fluoro-2-propyJ)pyrrole, N-(2-ch3oroethyJ)pyriO3e, N
- N-(8- bromooctyl)pyrroie N-(2-bromo-1-propyl)pyrrole, N-d-bromo-2-propyl)pyrroie, N- (2-iodoethyl)pyrrole, N-(3-iodopropyl)pyrrole, N-(4-iodobutyl)pyrrole, N-(6- iodohexyl)pyrrole, N-(8-iodooctyl)pyrrole, N-(2-iodo-1-propyl)pyrrole.
- N-(l-iodo-2- propyl)pyrroie; N-(cyanoalkyl)pyrroles e.g., N-(2-cyanoethyl)pyrroJe, N-(3- cyanopropyl)pyrro3e, N-(4-cyanobutyl)pyrrole, N-(6-cyanohexy1) ⁇ yrrole, N-(8- cyanoctyl)pyrrole, N-(2-cyano-1-propyl)pyrrole, N-(i-cyano-2-propyl)pyrrole; N- (azidoalkyl)pyrroles, e.g.
- the quenching with the functionalized N-substituted pyrrole covalently bonds the functionalized N- substitutcd pyrrole to tJie carbocationic center of the living or quasiliving polymer, thus functionalizing the living polymer.
- the number of functionalized N-substituted pyrrole functional groups on the polymer is determined by the number of initiation sites in the initiator used to create the living polymer or the polymer terminated with tert-alkyl halides.
- the functionalized N-substituted pyrrole-functionalized canonic polymers are nearly monodisperse, having substantially no EAS coupled polymers.
- polymers having at least one terminal N-substituted pyrrole moiety and these functionalized polymers can be derived from any suitable cationicaily polymerizabie monomers.
- the functionalized polymers can be homopolymers having substantially the same repeating monomer unit, or copolymers having two or more different repeating units. Particularly, AB block copolymers and ABA triblock copolymers can be formed.
- the functionalized polymers may also contain various hydrocarbyl headgroups based upon the selection of the initiator.
- the initiator can either mimic the growing chain end, e.g. a 1-phenylethyl derivative for polystyrene or 2,4,4- trimethylpentyl derivative for polyisobutylene, or may impart some desired group such as alikyl, cumyl. ester, silyl, etc. Additionally, by employing polyfunctional initiators, so called star polymers can be formed.
- examples of the functionalized polymers can be represented by, for a monofunctionai polymer, (Initiator residue)-(PoJyolefm)- (Functional N-substituted pyrrole) or, for a multifunctional initiator, (Initiator residue)-[(Polyolefm)-(Functional N-substituted pyrrole)] r where r equals the functionality of the initiator.
- coupling agents can be employed to link multiple polymer chains.
- "Initiator residue” represents the polyvalent radical (-CR a Rb>-Rc, with R 3 , Rb, Rc, and r as defined herein above.
- Polyolefm represents a polymer segment from at least one cationicaily polymerizable monomer; therefore, the functionalized N-substituted pyrrole polymers can be homopolymers, random or block copolymers, etc., and (Polyolefm) and (Functional N-substituted pyrrole) can be independently selected and thus be the same or different at each occurrence.
- l n some embodiments, as little as one equivalent of a functionalized N- substituted pyrrole per equivalent of chain ends during the quenching reaction is sufficient to carry out the functionalization. Greater amounts of functionalized N- substituted pyrrole are of course useful.
- the range of ratio of functionalized N-substituted pyrrole to chain end is 1 to 20 equivalents per chain end; in some embodiments it is 1 to 5 equivalents per chain end, and in some embodiments it is 1 to 2 equivalents per chain end. (Chain ends are determined by ascertaining the number of initiation sites per initiator molecule and multiplying that number by the number of initiator molecules present.) Typically the reaction is rapid and quantitative at various temperatures.
- the functionalized N-substituted pyrrole may be added neat or, in some embodiments, as a solution of the pyrrole in the chosen solvent for the polymerization.
- the addition may be singular and immediate or may be a more slowly controlled, metered addition.
- Additional Lewis acid catalyst, proton trap, and/or electron donor, or any combination thereof, which are typical components of the aforementioned living polymerization systems, may be added prior to, simultaneously with, or subsequently to the addition of the functionaiized N- substituted pyrrole.
- the Lewis acid does not irreversibly react with the N-substituted pyrrole.
- the product may be used in that form, or, in some embodiments, it may be modified by known chemistries to obtain a different product.
- the product is reacted with a reagent or reagents to form a compound of fonnula TTI;
- R 1 and R 2 are, independently in each -(CR 1 R 2 )- unit, hydrogen or alkyl from
- R is a monovalent polyolefin group; m is an integer from 2 to 20; and
- Z 2 is -NR 4 R 5 , -Nf(R 4 )(COR 5 )], -Nf(COR 4 )(COR 5 )], polyamino, polyamidoamino, polyaminoamido, -OR ⁇ , a polyether group, poiyetheramino, or -COORA; wherein R 4 and R 5 are each, independently, hydrogen, alkyl, or aryl; and Rg is hydrogen, alkyl, aryl, alkaryl, or aralkyl.
- Z 2 is -NR 4 R 5 .
- at least one ofR 4 and R 5 are hydrogen.
- R 4 is hydrogen and R 5 is aryl.
- -NR 4 R 5 is In further embodiments, -NR 4 R 5 is
- the reagent is a nucleophile or reducing agent. In some embodiments, the reagent is a nucleophiJe. In some embodiments, the reagent is NaN 3 or aniline. In some embodiments, the reagent is a reducing agent. In some embodiments, the reagents are hydrogen, palladium, and carbon. In some embodiments, the reagent is borane.
- R" is a divalent poly olefin group and R 3 is a monofimctional or polyfimctional carbocationic initiator residue of functionality r, wherein r is an integer from 1 to 8.
- R' is a polyisobutylene group. [00121] In some embodiments r is 2-3. In some embodiments r is 2.
- R 3 is , wherein R x is II or alkyl. In some embodiments R x is tert-butyl.
- R3 is
- R 3 is .
- R ⁇ is hydrogen.
- R « is not alkyl.
- Non- limiting examples of the various modification reactions that may be carried out include the following.
- Z 1 may be displaced as a leaving group by a nucleophilic reagent, thereby forming a covalent bond between the nucleophilic reagent and the carbon to which Z 1 was formerly bonded.
- groups containing unsaturations can undergo addition reactions with nucleophiles, thereby forming a covalent bond between the nucleophile and one of the atoms of Zj; in this case, Z 1 is not displaced from the polymer, but rather serves as a linking moiety to bind the nucleophile to the polymer.
- Z 1 may be reduced, oxidized, hydrogenated and/or hydrolyzed; for example, -N3 or -CN can be reduced by a hydride-containing or other reducing agent or by catalytic hydrogenation to from a primary amine, which is thereby attached to the pyrrole ring via a hydrocarbyl tether that either contains the original number of carbon atoms or the original number of carbon atoms plus one, respectively.
- Z 1 may be replaced by a halide or pseudohalide.
- Z 1 may be replaced by ammonia, a primary amine, or a secondary amine to yield a basic amine function at the polymer chain end.
- modification reactions may be performed in the same reactor used to react the living polymer with the functionalized N-substituted pyrrole, or they may be performed in a different reactor; that is, isolation of the functionalized N-substituted pyrrole-containing polymer prior to modification is optional.
- the product is typically subjected to conventional finishing steps which are known to those of skill in the art. These steps typically include deactivation of the Lewis acid catalyst by contacting with protic compounds such as water, an alcohol, ammonia, an amine, or mixtures thereof, a caustic/HjO wash and/or an acid/HbO wash to extract catalyst residue, a hydrocarbon/aqueous phase separation step wherein deactivated and extracted Lewis acid catalyst is isolated in the aqueous phase, and a water washing step to remove residual amounts of neutralized catalyst.
- protic compounds such as water, an alcohol, ammonia, an amine, or mixtures thereof
- a caustic/HjO wash and/or an acid/HbO wash to extract catalyst residue
- a hydrocarbon/aqueous phase separation step wherein deactivated and extracted Lewis acid catalyst is isolated in the aqueous phase
- a water washing step to remove residual amounts of neutralized catalyst.
- a class of products as provided herein has a narrow molecular weight distribution (Mw- 1 Mn). In some embodiments, the molecular weight distribution is about 4 or less. In some embodiments, the molecular weight distribution is about 2,5 or less. In further embodiments, the molecular weight distribution is 1.75 or less. In even further embodiments, the molecular weight distribution is 1.5 or less. In other embodiments, the molecular weight distribution is 1.2 or less.
- the ranges are from 1.01 up to 1.4.
- the methods described above produce polymers having a greater degree of functionalization than previously available by commercially viable processes.
- the degree of functionalization is about 70% or more.
- Tn some embodiments, the degree of functionalization is 80% or more.
- Tn further embodiments, the degree of functionalization is 90% or more.
- the degree of functionalization is 98% or more, as determined by proton NMR.
- the novel functionalized N-substituted pyrrole polymers described herein comprise terminally substituted polymers derived from any of the above-discussed cationically polymerizable monomers.
- the functionalized polymers will contain at least 4 monomer units per polymer chain, and will more usually be characterized by number average molecular weights of at least 350 and up to 100,000 g/mol or more.
- the molecular weight range can be determined for particular polymers.
- functionalized polymers range up to 100,000 g/moi for use as lubricant additives; and with specific ranges of 20,000 to 100,000 g/mol for use as viscosity improvers, and from 500 to 20,000 g/mol for use as dispersants and detergents.
- Low molecular weight polymers are useful in forming dispersants for lubricant additives and particularly useful are low molecular weight functional N-substituted pyrrole polymers.
- detergent and dispersant functionalized polymers have an average molecular weight of from about 500 to 5,000 g/mol. In some embodiments, detergent and dispersant functionalized polymers have an average molecular weight of from 500 to 3,000 g/mol. In some embodiments, detergent and dispersant functionalized polymers have an average molecular weight of from 700 to 2,000 g/mol. In even further embodiments, detergent and dispersant functionalized polymers have an average molecular weight of from 700 to 1,500 g/mol. Difunctional terminally functionalized polymers are useful as block segments for block copolymers, for example as soft segments in thermoplastic elastomers, and difunctional and polyfunctional terminally functionalized polymers are useful as chain elements in crosslinked network polymers.
- the molecular weight range is, in some embodiments, from 500 to 20,000 g/mol. In some embodiments, the molecular weight range is from 500 to 5,000 g/mol. In some embodiments, the molecular weight range is from 700 to 3,000 g/mol. In some embodiments, the molecular weights recited above are number average molecular weights measured by size exclusion chromatography equipped with multi-angle laser light scattering detection.
- the preparation of the polymers described herein can be conducted in a manner and under conditions to attain various molecular weight polymers. The polymers can be conveniently characterized based on molecular weight range. Polymers and copolymers of low, ⁇ 5,000 g/mol, intermediate, 5,000 to 30,000 g/mol, and high, i.e., 30,000 to 100,000 g/mol, molecular weights can be prepared.
- telechelic polylmers of the formula VI are provided herein:
- RJ and R 2 are, independently in each -(CRjR 2 )- unit, hydrogen or alkyl from
- Z 3 is -F, -Cl, -Br, -1, -At, -CN, -NC, -N 3 , -NCO, -OCN, -NCS, -SCN,
- R 4 and R 5 are each, independently, hydrogen, alkyl, or aryl; and R ⁇ is hydrogen, aryl, alkaryl, or aralkyl.
- Rj or R 2 of the -C(R]Ro)- group adjacent to Z 3 is hydrogen.
- Z 3 is a -CH 2 -.
- R 1 and R 2 are both hydrogen
- Tn some embodiments m is 2-6. Tn some embodiments, m is 2-4. In some embodiments, m is 2-3. In some embodiments m is 2.
- n is 2-1000. In some embodiments, n is 3-500. In some embodiments, n is 4-260, Tn some embodiments, n is 4-20. In some embodiments, n is 6-50. In some embodiments, n is 140-260.
- Z 3 is -Br, -CN, -N 3 , or -NR 4 R 5 .
- Z 3 is -NR 4 R 5 .
- Tn some embodiments, at least one
- R* is hydrogen and Rs is aryl.
- -NR 4 R 5 is .
- Tn some embodiments, -NR 4 R 5 is -NH 2 .
- m is 2-4
- Z 3 is -Br, -CN, -N 3 , or -NR 4 R 5
- R 1 and R 2 are both hydrogen.
- R 6 is hydrogen
- Tn some embodiments, provided herein are telechelic polymers of the formula VlI:
- R 1 and R 2 are, independently in each -(CR 1 R 2 )- unit, hydrogen and alkyl from 1 to 6 carbon atoms;
- R 3 is a polyfunctional carbocationic initiator residue of functionality r, where r can vary from 1 to 8; m is an integer from 2 to 20; n is independently, in each of the r chain segments, an integer from 0 to 2000; and
- Z 3 is is -F, -Cl, -Br, -1, -At 1 -CN, -NC, -N 3 , -NCO, -OCN, -NCS, -SCN, -NR 4 R 5 , -Nf(R 4 )(COR 5 )], -Nf(COR 4 )(COR 5 )I, polyamino, polyamidoamino, polyaminoamido, -OR ⁇ , a polyether group, polyetheramino, or -COOR 6 ; wherein R 4 and R 3 are each, independently, hydrogen, alkyl, or aryl; and R ⁇ is hydrogen, aryl, alkaryl, or aralkyl.
- At least one of Rj or R 2 of the -C(R]Ro)- group adjacent to Z 3 is hydrogen.
- the -(CR 1 R 2 )- group adjacent to Z 3 is a -CH 2 -.
- R 1 and R 2 are both hydrogen.
- m is 2-6.
- m is 2-4.
- Tn some embodiments, m is 2-3. In some embodiments, m is 2.
- n independently, in each of the r chain segments, is 2-1000. In some embodiments, n is 3-500. In some embodiments, n is 4-260. In some embodiments, n is 4-20. In some embodiments, n is 6-50. Tn some embodiments, n is 140-260.
- Z 3 is -Br, -CN, -N 3 , or -NR 4 R 5 .
- Z 3 is -NR 4 R 5 .
- at least one OfR 4 and R 5 are hydrogen.
- R 4 is hydrogen and R 5 is aryl.
- -NR 4 R 5 is . In some embodiments, -NR 4 R 5 is -NHo.
- m is 2-4
- Z 3 is -Br
- -CN -N ⁇ or -NR 4 R 5
- R 1 and R 2 are both hydrogen.
- r is 2-4. Tn some embodiments, r is 2-3. In some embodiments, r is 2.
- R ⁇ is hydrogen
- the compounds of formula IV are typically mixtures having the polyisobutyl group attached to the N-substituted pyrrole at the 2 and 3 position of the pyrrole.
- the compounds of formula V are typically mixtures have the polyisobutyJene groups attached to the N-substituted pyrrole moieties at the 2 and 3 position of the pyrrole.
- FUEL COMPOSITIONS AND CONCENTRATES [00150]
- the compounds described herein, particularly those represented by formula IV are useful as additives in hydrocarbon distillate fuels boiling in the gasoline or diesel range.
- the compounds of formula IV have a low molecular weight.
- n is selected from 2 to 20.
- the proper concentration of additive necessary in order to achieve the desired detergency and dispersancy varies depending upon the type of fuel employed, the presence of other detergents, dispersants, and other additives, etc. In some embodiments, the concentration of the additive is from about 25 to 7,500 ppm by weight, or in other embodiments, about 25 to 2,500 ppm by weight, in order to achieve the best results.
- the additive may be formulated as a concentrate, using an inert stable oleophilic organic solvent boiling in the range of from about 150 0 F to 400 0 F (or 65 °C to 200 °C).
- an aliphatic or an aromatic hydrocarbon solvent is used, such as benzene, toluene, xylene or higher-boiling aromatics or aromatic thinners.
- Aliphatic alcohols of from about 3 to 8 carbon atoms, such as isopropanol, isobutylcarbinol, n-butanol, and the like, in combination with hydrocarbon solvents are also suitable for use with the detergent-dispersant additive.
- the amount of the present additive will be from about 10 weight percent and generally will not exceed about 70 weight percent. In some embodiments, the amount of the additive will be from about 10 to 50 weight percent. In further embodiments, the amount of the additive will be from about 20 to 40 weight percent.
- additives described herein including, for example, oxygenates, such as t-butyl methyl ether, antiknock agents, such as methylcyclopentadienyl manganese tricarbonyl, and other dispersants/detergents, such as hydrocarbyl amines, hydrocarbyl poly(oxyalkylene) amines, hydrocarbyl poly(oxyalkylene) aminocarbamates, succinimides, or Mannich bases. Additionally, antioxidants, metal deactivators and demulsifiers may be present.
- oxygenates such as t-butyl methyl ether
- antiknock agents such as methylcyclopentadienyl manganese tricarbonyl
- dispersants/detergents such as hydrocarbyl amines, hydrocarbyl poly(oxyalkylene) amines, hydrocarbyl poly(oxyalkylene) aminocarbamates, succinimides, or Mannich bases.
- antioxidants, metal deactivators and demulsifiers may be present.
- a fuel-soluble, nonvolatile carrier fluid or oil may also be used with the functionalized polymers described herein.
- the carrier fluid is a chemically inert hydrocarbon-soluble liquid vehicle, which substantially increases the nonvolatile residue (NVR) or solvent-free liquid fraction of the fuel additive, while not overwhelmingly contributing to octane requirement increase.
- the carrier fluid may be a natural or synthetic oil, such as mineral oil, refined petroleum oils, synthetic polyalkanes and alkenes, including hydrogenated and unhydrogenated poly( ⁇ - olefms), and synthetic polyoxyalkylene-derived oils (such carrier fluids are described, for example, in U.S. Pat. No. 4,191,537), and polyesters, such as those described, for example, in U.S. Pat. Nos. 3,756,793 and 5,004,478, and in European Patent Application Nos. 356,726, published Mar. 7,1990, and 382,159, published Aug. 16, 1990. These carrier fluids are believed to act as a carrier for the fuel additives described herein and to assist in removing and retarding deposits.
- the earner fluid may also exhibit synergistic deposit control properties when ased in combination with a functionalized polymer described herein.
- the carrier fluids are employed in amounts ranging from about 25 to 7,500 ppm by weight of the hydrocarbon fuel, In some embodiments, the carrier fluids are employed in amounts ranging from about 25 to 2,500 ppm of the fuel. In some embodiments, the ratio of carrier fluid to deposit control additive will range from about 0.5:1 to 10:1. In further embodiments, the ratio of carrier fluid to deposit control additive will range from about 0.5: 1 to 4: 1. In even further embodiments, the ratio of carrier fluid to deposit control additive will range from about 0.5:1 to 2:1. When employed in a fuel concentrate, carrier fluids will generally be present in amounts ranging from about 20 to 60 weight percent or, in some embodiments, from about 30 to 50 weight percent.
- the compounds described herein, particularly those represented by formula IV, are useful as detergent and dispersant additives in lubricating oils.
- such compounds can be used in amounts of about 1 to about 10 percent by weight (on an actives basis) of the total composition, e.g., less than about 5 percent by weight (on an actives basis).
- Actives basis indicates that only the active ingredients of the polysuccinimides are considered when determining the amount of the additive relative to the remainder of a composition. Diluents and any other inactives, such as unreacted polyolefm, are excluded. Unless otherwise indicated, in describing the lubricating oil and final compositions or concentrates, active ingredient contents are intended with respect to the compounds.
- the lubricating oil used with the compounds described herein may be mineral or synthetic oils of lubricating viscosity or, in some embodiments, suitable for use in the crankcase of an internal combustion engine.
- Crankcase lubricating oils typically have a viscosity of about 1300 cSt at O 0 F (-17.8°C) to 22.7 cSt at 21O 0 F (99°C).
- Useful mineral oils include paraffinic, naphthenic and other oils that are suitable for use in lubricating oil compositions.
- Synthetic oils include both hydrocarbon synthetic oils and synthetic esters.
- Useful synthetic hydrocarbon oils include polymers of alpha olefins having suitable viscosity, e.g., the hydrogenated liquid oligomers of Ce to Cn alpha olefins, such as 1-decene trimer. Likewise, alkyl benzenes of proper viscosity such as didodecyi benzene can be used.
- Useful synthetic esters include the esters of both monocarboxylic acids and polycarboxylic acids as well as monohydroxy alkanols and polyols.
- Examples are didodecyi adipate, pentaerythritoJ tetracaproate, di-2-ethylhexyi adipate, dilauryisebacate and the like.
- Complex esters prepared from mixtures of mono and dicarboxylic acid and mono and dihydroxy alkanols can also be used.
- Blends of hydrocarbon oils and synthetic oils are also useful. For example, blends of 10 to 25 weight percent hydrogenated 1- decene trimer with 75 to 90 weight percent 150 SUS (100 0 F) mineral oil gives an excellent lubricating oil base.
- additives which may be present in the formulation include detergents (overbased and non-overbased), rust inhibitors, foam inhibitors, metal deactivators, pour point depressants, antioxidants, wear inhibitors, zinc dithiophosphates and a variety of other well known additives.
- detergents overbased and non-overbased
- rust inhibitors foam inhibitors
- metal deactivators metal deactivators
- pour point depressants antioxidants
- wear inhibitors zinc dithiophosphates
- zinc dithiophosphates zinc dithiophosphates
- the following additive components are examples of some of the components that can be favorably employed in the present invention. These examples of additives are provided to illustrate the present invention, but they are not intended to limit it:
- detergents which may be employed in the present invention include alkyl or alkenyl aromatic sulfonates, borated sulfonates, sulfurized or unsulfurized metal salts of m ⁇ lti-hydroxy alkyl or alkenyl aromatic compounds, alkyl or alkenyl hydroxy aromatic sulfonates, sulfurized or unsulfurized alkyl or alkenyl naphthenates, metal salts of alkanoic acids, metal salts of an alkyl or alkenyl multiacid, and chemical and physical mixtures thereof.
- Such agents include, but are not limited to, phosphates which comprise no more than 0.08 wt?/o of the lubricating oil composition , carbarmates, esters, and molybdenum complexes.
- Nonionic polyoxyethylene surface active agents polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, poiyoxyethylene octyl stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol mono-oleate, and polyethylene glycol mono-oleate.
- Viscosity Index Improvers Polymethacrylate type polymers, ethylene-propylene copolymers, styrene- isoprene copolymers, hydrated styrene-isoprene copolymers, polyisobutylene, and dispersant type viscosity index improvers.
- alkenyl succinimides alkenyl succinimides modified with other organic compounds, alkenyl succinimides modified by post-treatment with ethylene carbonate or boric acid, pentaerytbritols, phenate-salicyiates and their post-treated analogs, alkali metal or mixed alkali metal, alkaline earth metal borates, dispersions of hydrated alkali metal borates, dispersions of alkaline-earth metal borates, polyamide ashless dispersants and the like or mixtures of such dispersants.
- Anti-oxidants reduce the tendency of mineral oils to deteriorate in service which deterioration is evidenced by the products of oxidation such as sludge and varnish-like deposits on the metal surfaces and by an increase in viscosity.
- anti-oxidants useful in the present invention include, but are not limited to, phenol type (phenolic) oxidation inhibitors, such as
- Dipbenylamine-type oxidation inhibitors include, but are not limited to, alkylated diphenylamine, phenyl-alpha-naphthylamine, and alkylated-alpha-naphthylamine.
- Other types of oxidation inhibitors include metal dithiocarbamate (e.g., zinc dithiocarbamate), and 15-methylenebis(dibutyldithioearbamate).
- metal dithiocarbamate e.g., zinc dithiocarbamate
- 15-methylenebis(dibutyldithioearbamate) 15-methylenebis(dibutyldithioearbamate
- a compound described herein is added at from 0.1 to 5 percent by weight (on an active polymer basis) to the fluid or, in further embodiments at from 0.5 to 5 weight percent (on an active polymer basis).
- the compounds described herein can also be used in additive concentrates, which in some embodiments include from 90 to 10 percent, e.g., 20 to 60 weight percent, of an organic liquid diluent and from 10 to 90 weight percent, e.g., 80 to 40 weight percent (on a dry basis) of the compounds described herein.
- the concentrates contain sufficient diluent to make them easy to handle during shipping and storage.
- Suitable diluents for the concentrates include any inert diluent.
- the diluent is an oil of lubricating viscosity, so that the concentrate may be readily mixed with lubricating oils to prepare lubricating oil compositions.
- Suitable lubricating oils which can be used as diluents typically have viscosities in the range from about 1300 cSt at O 0 F (-17.8°C) to 22.7 cSt at 21O 0 F (99°C), although an oil of lubricating viscosity can be used.
- Figure 1 shows the 1 H NMR spectrum of the reaction product of quasiliving PIB and l-(2-chloroethyl)pyrrole.
- the spectrum indicates quantitative end-functionalization via electrophilic aromatic substitution.
- Quantitative substitution is indicated by the absence of resonances associated with PIB tert-chJoride end groups at 1.96 ppm (PIB-CH 2 -C(CH 3 ) ? -C1) and 1.68 ppm (PIB-CH 2 -C(CH 3 ) 2 -Cl).
- a new set of resonances appear at 1.65, 3.69, 4.11, 6.05, 6.40, and 6.56 ppm due to the product resulting from substitution at the 3-position of the pyrrole ring (major isomer).
- Substitution at the 2-position is also apparent due to resonances at 1.73, 3.73, 4.27, 5.90, 6.07, and 6.59 ppm.
- Figure 2 shows the 13 C NMR spectrum of the product. Functionalization of the end groups was confirmed by the disappearance of the resonances at 71.9 and 35.2 ppm, representing the quaternary and geminal dimethyl carbons, respectively, adjacent to the terminal tert-chloride group, and appearance of new peaks in both the aromatic and the aliphatic regions of the spectrum, as indicated by the peak assignments shown in Figure 2.
- TMPCl TMPCl
- 2.44 mL (4.22 g, 0.115 M) of TiCl 4 was charged to the reactor.
- the reaction was allowed to proceed for 10 min, and then a pre-chiiled solution of PyBr, prepared by dissolving 1.852 mL PyBr (2.70 g, 15.5 mmol) into 10 mL of hexane/CH ? Cl (60/40, v/v, 70°C), was added to the polymerization system.
- Figure 5 shows the 1 H NMR spectrum of the reaction product of quasiliving PIB and 1 -(2-bromoethyl)pyrrole, The spectrum indicates quantitative end-functionalization via electrophilic aromatic substitution. Quantitative substitution is indicated by the absence of resonances associated with PIB ter/-chloride end groups at 1.96 ppm (PIB-CH 2 -C(CH 3 ) 2 -C1) and 1.68 ppm (P1B-CH 2 -C(CH 3 ) 2 -C1). A new set of resonances appear at 1.65, 3.53, 4.18, 6.05, 6.40, and 6.56 ppm due to the product resulting from substitution at the 3-position of the pyrrole ring (major isomer). Substitution at the 2-position (minor isomer) is also apparent due to resonances at 1.73, 3.58, 4.31, 5.90, 6.07, and 6.59 ppm.
- Figure 6 shows the 13 C NMR spectrum of the product. Functionalization of the end groups was confirmed by the disappearance of the resonances at 71.9 and 35.2 ppm, representing the quaternary and geminal dimethyl carbons, respectively, adjacent to the terminal f ⁇ tf-chloride group, and appearance of new peaks in both the aromatic and the aliphatic regions of the spectrum, as indicated by the peak assignments shown in Figure 6.
- Quasiliving polymerization of IB with r-Bu-m-DCC as initiator was carried out within a dry nitrogen atmosphere glovebox, equipped with an integral, cryostated hexane/heptane bath according to the following procedure.
- Into a round- bottom flask equipped with a mechanical stirrer, infrared probe, and thermocouple were added 72 mL of CIhCX, 108 mL of w-hexane, and 0.1 16 mL (0.107 g, 5.3 xlO 3 M) of 2,6-lutidine.
- the mixture was allowed to equilibrate to -70 °C, and then 5.7 mL (4.0 g, 0.38 M) of IB was charged to the reactor. After thermal equilibration, 0.7182 g (0.013) of bDCC was added to the reactor. To begin the polymerization, 1.64 mL (2.84 g, 0.080 M) of TiCl 4 was charged to the reactor.
- Figure 9 shows the 1 H NMR spectrum of the reaction product of difunctionaj quasiiiving PIB and l-r2-chlorocthyl)pyrrole. Addition of the pyrrole moieties to the chain ends is indicated by the absence of resonances associated with PIB tert-chloride end groups at 1.96 ppm and 1.68 ppm. A new set of resonances appear at 1.65, 3.69. 4.11, 6.05, 6.40, and 6.56 ppm due to the product resulting from substitution at the 3-position of the pyrrole ring (major isomer). Substitution at the 2- position (minor isomer) is also apparent due to resonances at 1.73, 3.73, 4.27, 5.90, 6.07, and 6.59 ppm.
- the aromatic initiator residue from bDCC provided an internal reference for quantification of end group functionality by 1 H NMR.
- various end group resonance areas were integrated and compared to the integrated area of the aromatic protons (m) in Figure 9.
- Table i the results indicated essentially quantitative functionalization of the chain ends.
- integration of the methylene protons adjacent to the chloride group (g + a) and to the nitrogen of the pyrrole ring (h + b) yielded percent end group functionality of 101 %. Integration of the various pyrrole ring hydrogens yielded 90-92% end group functionality.
- the aromatic initiator residue from bDCC provided an internal reference for quantification of end group functionality by 1 H NMR.
- various end group resonance areas were integrated and compared to the integrated area of the aromatic protons (m) in Figure 11.
- Table 2 the results indicated essentially quantitative functionaJization of the chain ends.
- integration of the methylene protons adjacent to the bromide group (h + b) and to the nitrogen of the pyrrole ring (g + a) yielded percent end group functionality of 101%. Integration of the various pyrrole ring hydrogens yielded 90-93% end group functionality.
- the polymer was dissolved in hexane, and the resulting solution was washed with methanol in a separatory funnel. The polymer was then precipitated one time into methanol from hexane. The swollen precipitate was re-dissolved in hexane, and the resulting solution was washed with water in a separatory funnel and dried over MgSO 4 . The dried solution was passed through a column of silica gel. The polymer was freed of hexane by distillation using a rotary evaporator and final vacuum drying in a vacuum oven at room temperature.
- N-(3-Bromopropyl)pyrrole (PyBrP) was synthesized by N-alkylation of pyrrolyl sodium salt with 1,3-dibromopropane in DMSO and purified by fractional distillation.
- the pyrrole ring protons of the 3-PIB isomer were observed as multiplets at 6.02, 6.38, and 6.55 ppm, and those of the 2-PIB isomer were observed at 5.88, 6.05 and 6.59 ppm. Singlets at 1.65 and 1.73 ppm were assigned to the ultimate methylene unit of the PIB chain in the 3- and 2-PIB isomer, respectively.
- N-(3-Bromopropyl)pyrrole (PyBrP) was synthesized by N-alkylation of pyrrolyl sodium salt with 1,3-dibromopropane in DMSO and purified by fractional distillation.
- Figure 14 shows the 1 H NMR spectrum of the reaction product of difunctional quasiliving PIB and l-(3-bromopropyl)pyrrole. Addition of the pyrrole moieties to the chain ends is indicated by the absence of resonances associated with PIB fer/-chloride end groups at 1.96 ppm and 1.68 ppm. A new set of resonances appears at 1.65, 2.21, 3.29, 3.99, 6.02, 6.38, and 6.55 ppm due to the product resulting from substitution at the 3-position of the pyrrole ring (major isomer). The product resulting from substitution at the 2-position (minor isomer) is observed at 1.73, 2.35, 3.50, 4.13, 5.88, 6.05, and 6.59 ppm.
- Quasiliving polymerization of TB with bDCC as initiator was carried out within a dry nitrogen atmosphere glovebox, equipped with an integral, cryostated hexane/heptane bath according to the following procedure.
- Into a round-bottom flask equipped with a mechanical stirrer, infrared probe, and thermocouple were added 680 mL of CII 3 Cl, 1,020 mL of ⁇ -hexane, and 0.667 mL (0.614 g, 3.2 xlO -3 M) of 2,6- lutidine.
- the mixture was allowed to equilibrate to -70 °C and then IB, 85.95 mL (60.0 g, 0.59 M) was charged to the reactor. After thermal equilibration, 7.494 g (0.013 M) of bDCC was added to the reactor. To begin the polymerization, 17.16 mL (29.7 g, 0.086 M) of TiCl 4 was charged to the reactor. The reaction was allowed to proceed for 55 min, and then a pre-chilled solution of PyBr, prepared by dissolving 12.97 mL PyBr (18,9 g, 109 mmol) into a mixture of 15 mL of hexane and 10 mL CH3CI, was added to the polymerization system.
- the swollen precipitate was re-dissolved in hexane, and the resulting solution was washed with water in a separatory funnei and dried over MgSO 4 .
- the dried solution was passed through a column of silica gel.
- the polymer was freed of hexane by distillation using a rotary evaporator and final vacuum drying in a vacuum oven at room temperature.
- Monofunctional tert-chloride-terminated PIB was prepared within a dry nitrogen atmosphere glovebox, equipped with an integral, cryostated hexane/heptane bath, according to the following procedure.
- Into a round-bottom flask equipped with a mechanical stirrer, infrared probe, and thermocouple were added 654.5 mL of CH 3 Cl, and 0.58 mL (0.53 g, 6,2 xlO -3 M) of 2,6-lutidine. The mixture was allowed to equilibrate to -70 °C and then IB, 97.15 mL (67.81 g, 1.51 M) was charged to the reactor.
- Quantitative functionalization was indicated by complete disappearance of the ter/-chloride peaks at 1.96 ppm and 1.68 ppm and appearance of two triplets of equal area, centered at 3.52 and 4.19 ppm, which represent the methylene groups bonded to the bromine and nitrogen atoms, respectively, of the 3-PIB isomer.
- Methylene signals for the 2-PTB-isomer also appeared centered at 3.58 and 4.31 ppm.
- the signals for the pyrrole ring protons and the PlB ultimate methylene protons were present and exhibited the same pattern observed for the product obtained with the PyBr quencher in the previous examples above. No olefin was detected.
- MonofuDctional primary chloride-terminated PIB was prepared within a dry nitrogen atmosphere glovebox, equipped with an integral, cryostated hexane/heptane bath, according to the following procedure.
- Into a round-bottom flask equipped with a mechanical stirrer, infrared probe, and thermocouple were added 340 mL of CII 3 Cl, 510 mL of n-hexane, and 0.33 mL (0.30 g, 3.1 xlO -3 M) of 2.6-lu ⁇ idine. The mixture was allowed to equilibrate to -70 °C and then IB, 47.5 mL (33.2 g, 0.65 M) was charged to the reactor.
- Figure 16 shows the 1 H NMR spectrum of the resulting polymer with peak assignments. Addition of the azide was indicated by the disappearance of the peaks at 3.69 (3-PIB-Py-CH 2 -CH 2 -Cl), 3.73 (2-PIB-Py-CH 2 -CH 2 -Cl), 4.11 (3-PIB-Py-CH 2 - CH 2 -Cl), and 4.27 ppm (2-PIB-Py-CH 2 -CH 2 -Cl) and appearance of new peaks at 3.52 and 3.95 ppm (3-isomer, major) and 3.64 and 4.13 ppm (2-isomer, minor) due to presence of the l-(2-azidoethyl)pyrrole moieties at the chain ends.
- Figure 18 shows the 1 H NMR spectrum of the resulting polymer with peak assignments. Addition of the capping agent was indicated by the disappearance of the peaks at 1.96 ppm (-PIB-CH 2 -C(CH 3 ) 2 -C1) and 1.68 ppm (-PIB-CH 2 -C(CH 3 ) 2 -C1) and appearance of new peaks at 1.66, 2.72, 4.11, 6,07, 6.40 and 6,57 ppm (3-isomer, major) and 1.71, 2.80, 4.29, 5.90, 6.10 and 6.60 ppm (2-isomer, minor) due to presence of the l-(2-cyanoethyl)pyrrole moieties at the chain ends.
- Figure 19 shows the partial 1 H NMR spectra of aliquots removed from the reactor at various times.
- the progress of quenching by 1 -(2-eyanoethyl) pyrrole can be observed by the disappearance of the methyl protons (1.68 ppm) and the methylene protons (1.96 ppm) adjacent to the terminal tert-chloride groups of the quasiliving PlB precursor. Functionalization was complete within 20 min.
- the GPC traces of the PIB prior to and after end-capping were essentially the same, indicating the absence of any coupling reactions or polymer degradation (Figure 20).
- the aromatic initiator residue from bDCC provided an internal reference for quantification of end group functionality by 1 H NMR.
- various end group resonance areas were integrated and compared to the integrated area of the aromatic protons (m) in Figure 18.
- Table 4 the results indicated essentially quantitative functionaJization of the chain ends.
- integration of the methylene protons adjacent to the cyano group (h + b) and to the nitrogen of the pyrrole ring (g + a) yielded percent end group functionality of 103 and 104%. Integration of the various pyrrole ring hydrogens yielded 96% end group functionality.
- l-(2-Azidoethy])pyrrole was prepared by reaction of excess NaN3 with 1 - (2-bromoethyl)pyrrole in a 50/50 (v/v) heptane/dimethylformamide mixture at 90°C for 24 h.
- Peak integration analysis (Table 5) indicated high functionalizalion of the chain ends. Integration of the methylene protons adjacent to the azido group (h + b) and to the nitrogen of the pyrrole ring (g + a) yielded percent end group functionality of 98-99%. Integration of the b protons (-CH 2 -CII 2 -N 3 of the 3-isomer) yielded the fraction of 3 isomer [b/(h + ⁇ b)] as 0.62; likewise integration of the 112 proton of the 3 isomer (e) yielded the fraction of 3 isomer [e/(k + e)] as 0.61. Functionalization with azido groups was not perfectly quantitative due to the presence of mixed exolendo olefins, estimated to be about 1-2%. Table 5
- the methylene protons of the ethylene bridge were used to monitor reaction conversion.
- the methylene protons adjacent to pyrrole were observed at 4, 1 (2-isomer, minor) and 3.8 (3-isomer, major), and the methylene protons adjacent to the amine group were observed at 3.1 (2-isomer, minor) and 3.0 (3-isomer, major). No residual resonances due to azide-PIB were observed.
- Soot dispersancy tests were also carried out on Examples 17 and 18, as well as Comparative Example A at different dosages in the soot thickening bench test. The details of this test are described in U.S. Patent No. 5,716,912, the entire contents of which are incorporated by reference herein.
- soot thickening bench test the kinematic viscosity of an oil is measured before and after the introduction of homogeneously dispersed carbon black. Since carbon black is known to agglomerate, this normally causes an increase in the kinematic viscosity of the oil. An additive that is effective in preventing the agglomeration of carbon black will generally perform well at soot dispersancy.
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US8063154B2 (en) * | 2008-06-24 | 2011-11-22 | The University Of Southern Mississippi | Preparation of exo-olefin terminated polyolefins via quenching with alkoxysilanes or ethers |
US8344073B2 (en) | 2009-01-16 | 2013-01-01 | The University Of Southern Mississippi | Functionalization of polyolefins with phenoxy derivatives |
US8394898B2 (en) * | 2009-07-31 | 2013-03-12 | The University Of Southern Mississippi | In situ formation of hydroxy chain end functional polyolefins |
US8492491B2 (en) | 2010-06-10 | 2013-07-23 | Chevron Oronite Company Llc | Methods for producing telechelic polyolefins from terpene initiators |
US8592527B2 (en) | 2010-06-14 | 2013-11-26 | University Of Southern Mississippi | Vinyl ether end-functionalized polyolefins |
US8334243B2 (en) * | 2011-03-16 | 2012-12-18 | Afton Chemical Corporation | Lubricant compositions containing a functionalized dispersant for improved soot or sludge handling capabilities |
US8969484B2 (en) | 2011-07-08 | 2015-03-03 | Chevron Oronite Company Llc | Methods of producing mono- and multi-functional polymers from terpene-based initiators |
US9243203B2 (en) * | 2012-11-30 | 2016-01-26 | Chevron Oronite Company Llc | Copolymers of polyaminopolyolefins and polyanhydrides and methods of their preparation |
GB2515071B (en) * | 2013-06-13 | 2015-12-09 | Reckitt Benckiser Brands Ltd | Novel composition for a foot-soaking bath |
FR3013712B1 (en) * | 2013-11-22 | 2016-09-09 | Herakles | POLYMERS WITH TERMINAL AZOTURE FUNCTIONS, THEIR OBTAINING; SOLID PROPERGOLS OBTAINED FROM SAID POLYMERS |
WO2017059201A1 (en) | 2015-10-01 | 2017-04-06 | The University Of Southern Mississippi | Methods of preparing functionalized polyolefins |
JP2018168356A (en) * | 2017-03-29 | 2018-11-01 | 昭和電工株式会社 | Lubricant composition and its manufacturing method |
JP2020111624A (en) * | 2017-05-09 | 2020-07-27 | 公益財団法人川崎市産業振興財団 | Polymer and production method of polymer |
CN111094394A (en) | 2017-09-18 | 2020-05-01 | 雪佛龙奥伦耐有限责任公司 | Polyolefin dispersants and methods of making and using the same |
CN115161084A (en) * | 2022-07-08 | 2022-10-11 | 赵明晖 | PNF fuel additive for preventing piston ring from being stuck |
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Also Published As
Publication number | Publication date |
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US20140031497A1 (en) | 2014-01-30 |
JP5717719B2 (en) | 2015-05-13 |
WO2010117619A3 (en) | 2011-02-03 |
US8552122B2 (en) | 2013-10-08 |
SG174372A1 (en) | 2011-10-28 |
CN102356114B (en) | 2014-06-25 |
WO2010117619A2 (en) | 2010-10-14 |
CA2757267A1 (en) | 2010-10-14 |
CN102356114A (en) | 2012-02-15 |
EP2414432B1 (en) | 2017-05-31 |
EP2414432A4 (en) | 2012-10-17 |
US20100249001A1 (en) | 2010-09-30 |
JP2012524822A (en) | 2012-10-18 |
US9315595B2 (en) | 2016-04-19 |
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